Propylene polymer and composition containing the same, molded object and laminate comprising these, and processes for producing propylene polymer and composition containing the same

ABSTRACT

A propylenic polymer according to the present invention or a composition thereof have an excellent melt flowability and contains a less amount of stickiness-causing components, and also has a low modulus and is pliable, and is capable of providing a transparent molded article, thus being useful as a substitute for a pliable vinyl chloride resin. In addition, a molded article made therefrom exhibits an excellent heat seal performance at a low temperature, and is excellent in terms of transparency and rigidity. Specifically, it has an isotactic pentad fraction (mmmm), which indicates a stereoregularity, of 30 to 80%, a molecular weight distribution (Mw/Mn) of 3.5 or less and an intrinsic viscosity [η] of 0.8 to 5 dl/g.

TECHNICAL FIELD

The present invention relates to a propylenic polymer which has anexcellent melt flowability, contains a less amount of stickiness-causingcomponents, has a low modulus and is pliable, and is capable ofproviding a transparent molded article, thus being useful as asubstitute for a pliable vinyl chloride resin, a method for producingthe same, a propylenic resin composition and a molded article madetherefrom; a propylenic polymer composition which is excellent in termsof heat seal performance at a low temperature and moldability, and iscapable of providing a film or a molded article which is excellent interms of transparency and rigidity, as well as a molded article, a filmor a laminated article made therefrom.

More particularly, the invention relates to a polypropylenic polymercomposition which is obtained by a polymerization using a metallocenecatalyst, has a narrow molecular weight distribution and exhibits anexcellent moldability and secondary processability (low temperature heatseal performance) and also to a film made therefrom.

Furthermore, the invention relates to a transition metal compound and apolymerization catalyst employed preferably in a polymerization of anolefinic resins mentioned above.

BACKGROUND OF THE INVENTION

A vinyl chloride resin which has widely been employed as a pliablesynthetic resin is known to generate a hazardous material during acombustion process, because of which a development of a substitute of avinyl chloride resin is desired. One substitute for a pliable vinylchloride resin is a propylenic polymer. While a propylenic polymer isproduced in the presence of various catalyst, a propylenic polymerproduced using a conventional catalyst system involves adisadvantageously increased amount of stickiness-causing components as aresult of an attempt to impart a pliability (i.e. a low modulus). Theincrease in the amount of stickiness-causing atactic polypropylenes(hereinafter referred to as APP) leads to a deteriorated surfacecondition of a molded article obtained.

On the other hand, an application of a molded article in a form of asheet or a film to a food product or a medical use may involve variousproblems. Accordingly, a propylenic polymer having a more satisfactorilyweighed relationship between a low level of the modulus and the quantityof the stickiness-causing components is desired.

Since a propylenic polymer generally has a greater supercooling degreerequired for initiating a crystallization when compared with anethylenic polymer, it provides a resin characterized by a lowercrystallization temperature even if it has a same melting point.Accordingly, it may cause a problematically poor molding performanceespecially with a heat seal grade product having a low melting point. Inan attempt to reduced the heat seal temperature, a method for reducingthe stereoregularity index of a propylenic polymer is employed, or acopolymer with other olefins is used. Among those produced in suchattempt, a conventional low stereoregular propylenic polymer obtained byusing a Ziegler catalyst system has a broad stereoregularitydistribution, and an attempt to obtain a pliable polymer (i.e. having alow modulus) results in an increase in the amount of stickiness-causingcomponents, including one derived from APP which causes a poor physicalproperty of a low stereoregular propylenic polymer, such as a poorsurface condition of a molded article once such propylenic polymer ismolded. Thus, it is desired to obtain a film, a fiber, a sheet or amolded article in which a low melting point and a very narrowstereoregularity distribution possessed by a low stereoregular polymerare still preserved and which has an excellent transparency and a lowtemperature heat seal performance and is highly rigid.

Other disadvantageous characteristics of a propylenic polymer include ahigh glass transition temperature Tg (about 0° C.), due to which theimpact resistance at a low temperature (e.g. −30° C.) is problematicallypoor.

Recently, an olefin polymer produced by using a metallocene catalyst wasalso proposed, but a metallocene catalyst has a limited active center,which results in a narrow molecular weight distribution of a polymerobtained, which is suitable to a precise injection molding or anordinary injection molding and can preferably be employed to mold afiber, but is not always satisfactory when applied to a heat molding, anextrusion, a blow molding or a molding of a foam or a film. An LLDPE(linear low density polyethylene) obtained using a metallocene alsoinvolves the problems of poor transparency and surface condition,although it has a pliability.

DISCLOSURE OF THE INVENTION

An objective of the invention is to provide a propylenic polymer whichhas an excellent melt flowability, contains a less amount ofstickiness-causing components, has a low modulus and is pliable, and iscapable of providing a transparent molded article, a method forproducing the same, a propylenic resin composition and a molded articlemade therefrom; a propylenic polymer composition which is excellent interms of heat seal performance at a low temperature and moldability, andis capable of providing a film or a molded article which is excellent interms of transparency and rigidity, as well as a molded article, a resinmodifier, a film or a laminated article made therefrom.

Another objective of the invention is to provide a polypropylenicpolymer composition which is obtained by a polymerization using ametallocene catalyst, has a narrow molecular weight distribution andexhibits an excellent moldability and secondary processability (lowtemperature heat seal performance) as well as a film made therefrom, andalso to provide a transition metal compound, a polymerization catalystand a method for production which are employed preferably in apolymerization of an olefinic resins mentioned above.

We made an effort and discovered that various parameters such as anisotactic pentad fraction (mmmm), molecular distribution, intrinsicviscosity [η] and stereoregularity index (P) are related closely tovarious properties of a propylenic polymer, and finally established theinvention.

Thus, the present application consists of the following inventions.

I. First invention

1. A propylenic polymer which is a propylene homopolymer having anisotactic pentad fraction (mmmm), which indicates a stereoregularity, of30 to 80%, a molecular weight distribution (Mw/Mn) of 3.5 or less and anintrinsic viscosity [η] of 0.8 to 5 dl/g;

2. A propylenic polymer which is a propylenic copolymer produced bycopolymerising propylene and ethylene and/or an α-olefin having 4 to 20carbon atoms having a stereoregularity index (P) of 55 to 90% by mole, amolecular weight distribution (Mw/Mn) of 3.5 or less and an intrinsicviscosity [71] of 0.8 to 5 dl/g;

3. A method for producing a propylenic polymer of above 1 whereinpropylene is homopolymerized in the presence of a polymerizationcatalyst comprising (A) a transition metal compound represented byFormula (I):

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group, is crosslinked witheach other via A¹ and A² and may be same to or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be same or different, and each may be crosslinked withother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be same or different, and each may be crosslinkedwith other Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group having two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AIR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be same to or different from each other; q is an integer of1 to 5 and represents [(valency of M)−2], and r is an integer of 0 to 3and(B) a component selected from (B-1) a compound capable of forming anionic complex by reacting with a transition metal compound as acomponent (A) or a derivative thereof and (B-2) an aluminoxane;

4. A method for producing a propylenic polymer of above 2 whereinpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomsare copolymerized in the presence of a polymerization catalystcomprising a transition metal compound represented by Formula (I) shownabove and (B) a component selected from (B-1) a compound capable offorming an ionic complex by reacting with a transition metal compound asa component (A) or a derivative thereof and (B-2) an aluminoxane;

5. A molded article made from a propylenic polymer described above;

6. A propylenic polymer composition obtained by incorporating into apropylenic polymer of above 1 a nucleating agent at a level of 10 ppm orhigher;

7. A propylenic polymer composition obtained by incorporating into apropylenic polymer of above 2 a nucleating agent at a level of 10 ppm orhigher;

8. A propylenic polymer composition of above 6 or 7 wherein a propylenicpolymer has a crystallization temperature (Tc(° C.)) and a melting point(Tm (° C.)), as determined by a differential scanning calorimeter, whichare in the relationship represented by the formula: Tc≧0.75Tm−15;

9. A molded article and a film made from a propylenic polymercomposition of any of 6 to 8 described above; and,

10. A laminated article comprising as at least one layer component apropylenic polymer composition of any of 6 to 8 described above.

II. Second Invention

1. A propylenic polymer satisfying the following requirements (1) and(2):

(1) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(2) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140);

2. A propylenic polymer satisfying the following requirements (1) to(3):

(1) the amount of the components which are dissolved out at 0° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140);

3. A propylene homopolymer satisfying the following requirements (1) to(3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;

4. A propylenic copolymer satisfying the following requirements (1) and(2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at oC or lower(W25) in a temperature-raising chromatography ranges from 20 to 100% byweight.

5. A propylene homopolymer of above 1 or 2 or a propylenic copolymer ofabove 4 having a molecular weight distribution (Mw/Mn) determined by agel permeation chromatography (GPC) of 4 or less and/or an intrinsicviscosity [η] determined in a tetralin solvent at 135° C. of 0.5 to 15.0dl/g;

6. A method for producing a propylene homopolymer of above 1, 2, 3 or 5wherein propylene is homopolymerized in the presence of a polymerizationcatalyst comprising (A) a transition metal compound represented byFormula (I) shown below and (B) a component selected from (B-1) acompound capable of forming an ionic complex by reacting with atransition metal compound as a component (A) or a derivative thereof and(B-2) an aluminoxane;

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group, is crosslinked witheach other via A¹ and A² and may be same to or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be same or different, and each may be crosslinked withother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be same or different, and each may be crosslinkedwith other Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group having two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be same to or different from each other; q is an integer of1 to 5 and represents [(valency of M)−2], and r is an integer of 0 to 3;

7. A method for producing a propylenic copolymer of above 4 or 5 whereinpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomsare copolymerized in the presence of a polymerization catalystcomprising (A) a transition metal compound represented by Formula (I)shown below and (B) a component selected from (B-1) a compound capableof forming an ionic complex by reacting with a transition metal compoundas a component (A) or a derivative thereof and (B-2) an aluminoxane;

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group, is crosslinked witheach other via A¹ and A² and may be same to or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be same or different, and each may be crosslinked withother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be same or different, and each may be crosslinkedwith other Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group having two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be same to or different from each other; q is an integer of1 to 5 and represents [(valency of M)−2], and r is an integer of 0 to 3;

8. A propylenic resin composition obtained by adding a nucleating agentto a propylenic polymer, a propylene homopolymer or a propyleniccopolymer of any of above 1 to 5;

9. A molded article obtained by molding a propylenic polymer, apropylene homopolymer, a propylenic copolymer or a propylenic resincomposition of any of above 1 to 5 or 8; and,

10. A propylenic resin modifier comprising a propylenic polymer, apropylene homopolymer or a propylenic copolymer of any of above 1 to 5.

III. Third Invention

1. A propylenic polymer satisfying the following requirements (1) to(3):

(1) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight;(2) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140); and,

(3) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) ranges from 2.5 to 14.0 and theintrinsic viscosity [η] determined in a decalin solvent at 135° C.ranges from 0.5 to 15.0 dl/g;

2. A propylene homopolymer satisfying the following requirements (1) to(3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 85% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) ranges from 2.5 to 14.0 and theintrinsic viscosity [η] determined in a decalin solvent at 135° C.ranges from 0.5 to 15.0 dl/g;

3. A propylenic copolymer satisfying the following requirements (1) and(2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and, (2) the molecular weight distribution (Mw/Mn)determined by a gel permeation chromatography (GPC) ranges from 2.5 to14.0 and the intrinsic viscosity [η] determined in a decalin solvent at135° C. ranges from 0.5 to 15.0 dl/g;

4. A propylenic polymer, a propylene homopolymer or a propyleniccopolymer of any of above 1 to 3 having a complex viscosity coefficient[η*](Pa·s) and an intrinsic viscosity [η] (dl/g) at the frequency ω,based on the frequency distribution determination of the meltviscoelasticity, of 100 rad/sec which are in the relationshiprepresented by the formula:

η*<159η+743;

5. A method for producing a propylenic polymer, a propylene homopolymeror a propylenic copolymer of any of above 1 to 4 wherein apolymerization is effected by a multi-step polymerization processcomprising at least a step in which propylene is homopolymerized, orpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomsare copolymerized in the presence of a polymerization catalystcomprising:

(A) a transition metal compound represented by Formula (I) shown belowand (B) a component selected from (B-1) a compound capable of forming anionic complex by reacting with a transition metal compound as acomponent (A) or a derivative thereof and (B-2) an aluminoxane.

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an aide group, a phosphide group, aπ-binding hydrocarbon group and a silicon-containing group, iscrosslinked with each other via A¹ and A² and may be same to ordifferent from each other, X denotes a σ-binding ligand, and, when twoor more Xs are present they may be same or different, and each may becrosslinked with other X, E¹, E² or Y; Y denotes a Lewis base, and, whentwo or more Ys are present they may be same or different, and each maybe crosslinked with other Y, E¹, E² or X, each of A¹ and A² denotes adivalent crosslinking group having two ligands including a hydrocarbongroup having 1 to 20 carbon atoms, a halogen-containing hydrocarbongroup having 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be same to or different from each other; q is an integer of1 to 5 and represents [(valency of M)−2], and r is an integer of 0 to 3;and,

6. A molded article obtained by molding a propylenic polymer, apropylene homopolymer or a propylenic copolymer of any of above 1 to 4.

IV. Fourth Invention

1. A propylenic resin composition comprising a propylene homopolymer (a)and/or a propylenic copolymer (a′) and satisfying the followingrequirements [1] to [3]:

[1] the amount of the components extracted with a boiling diethyletherranges 1 to 99% by weight;[2] in a propylene homopolymer (a), a component extracted with a boilingdiethylether satisfies the following requirements (1) to (3):(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight; and,[3] in a propylenic copolymer (a′), a component extracted with a boilingdiethylether satisfies the following requirements (4) and (5):(4) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and, (5) the amount of the components which aredissolved out at 25° C. or lower (W25) in a temperature-raisingchromatography ranges from 20 to 100% by weight;

2. A propylenic resin composition comprising 1 to 99% by weight of apropylenic polymer [I] and 99 to 1% by weight of a polyolefin [II] inwhich said propylenic polymer [1} satisfies the following requirements(1) to (3):

(1) the amount of the components which are dissolved out at 0° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140);

3. A propylenic resin composition comprising 1 to 99% by weight of apropylene homopolymer (a) and 99 to 1% by weight of a polyolefin [II] inwhich said propylene homopolymer (a) satisfies the followingrequirements (1) to (3):

(1) the meso-pentad fraction (mmmm(in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;

4. A propylenic resin composition comprising 1 to 99% by weight of apropylenic copolymer (a′) and 99 to 1% by weight of a polyolefin [II] inwhich said propylene homopolymer (a′) satisfies the followingrequirements (1) and (2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;

5. A propylenic resin composition of any of above 1 to 4 in which apropylene homopolymer (a) and a propylenic copolymer (a′) eachindependently satisfy the following requirements (1) and/or (2):

(1) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) is 4 or less; and,(2) the intrinsic viscosity [η]) determined in a tetralin solvent at135° C. ranges from 0.5 to 15.0 dl/g;

6. A propylenic resin composition of any of above 2 to in which apolyolefin [II] has a crystallization temperature (Tc(° C.)) andconsists of a propylenic polymer (b) having a Tc≧0° C. and/or an olefinpolymer (b′) having a glass transition temperature Tg≦−10° C.;

7. A method for producing a propylenic resin composition of any of above1 to 6 comprising homopolymerizing propylene or copolymerizing propyleneand ethylene and/or an α-olefin having 4 to 20 carbon atoms in thepresence of a co-catalyst comprising a metallocene catalyst comprising:

(A) a transition metal compound represented by Formula (I) shown belowand (B) (B-1) a compound capable of forming an ionic complex by reactingwith a transition metal compound as a component (A) or a derivativethereof or (B-2) an aluminoxane and at least one other catalyst.

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group, is crosslinked witheach other via A¹ and A² and may be same to or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be same or different, and each may be crosslinked withother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be same or different, and each may be crosslinkedwith other Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group having two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₄—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be same to or different from each other; q is an integer of1 to 5 and represents [(valency of M)−2], and r is an integer of 0 to 3;

8. A method for producing a propylenic resin composition of any of above1 to 6 comprising homopolymerizing propylene or copolymerizing propyleneand ethylene and/or an α-olefin having 4 to 20 carbon atoms in amulti-step polymerization process comprising at least a processemploying a metallocene catalyst of above 7; and,

9. A molded article made from a propylenic resin composition of any ofabove 1 to 6.

V. Fifth Invention

1. A propylenic resin composition having a peak top temperature (Tc(°C.)) on the side of the maximum temperature on a crystallization curveand a differential calorie (ΔHm(J/g)) on a fusion curve, as determinedby a differential scanning calorimeter (DSC), which are in therelationship represented by the following formula (I-1):

Tc≧(1/4)·ΔHm+90  (1-1)

and having a frequency (ω(rad/sec)) at which the storage modulus(G′(Pa)) and the loss elasticity (G″(Pa)) based on the frequencydistribution determination of the melt viscoelasticity become equal toeach other and a ΔHm, which are in the relationship represented by thefollowing formula (2-1):

ω≦(1/10)·ΔHm+15  (2-1);

2. A propylenic resin composition of above 1 comprising 1 to 99% byweight of a propylenic polymer [I] satisfying the following requirements(1) to (3) and 99 to 1% by weight of a crystalline propylenic polymer[II]:

(1) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/g) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140);

3. A propylenic resin composition of above 1 comprising 1 to 99% byweight of a propylene homopolymer [a] satisfying the followingrequirements (1) to (3) and 99 to 1% by weight of a crystallinepropylenic polymer [II]:

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;

4. A propylenic resin composition of above 2 or 3 in which a propylenicpolymer [I] of above 2 or a propylene homopolymer [a] of above 3satisfies the following requirements (1) and/or (2):

(1) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) is 4 or less; and,(2) the intrinsic viscosity [η] determined in a tetralin solvent at 135°C. ranges from 0.5 to 15.0 dl/g;

5. A propylenic resin composition of any of above 2 to 4 in which apropylenic polymer [I] of above 2 or a propylene homopolymer [a] ofabove 3 exhibits no melting point (Tm(° C.)) in DSC;

6. A film or a sheet having a layer produced by a propylenic resincomposition of any of above 1 to 5; and,

7. A film or a sheet of above 6 whose haze determined in accordance withJIS K7105 is 10% or less.

VI. Sixth Invention

1. A polypropylenic resin composition comprising (A) 99 to 50% by weightof a propylene homopolymer having the following characteristics (a1) to(a4):

(a1) the intrinsic viscosity [η] is 0.5 to 5.0 dl/g;(a2) the molecular weight distribution (Mw/Mn) is 3.5 or less;(a3) the isotactic pentad fraction (mmmm (in percentage terms by mole))is 40 to 99% by mole; and,(a4) the isotactic pentad fraction (mmmm(in percentage terms by mole))and the melting point (Tm(° C.)) are in the relationship represented bythe following formula (I):

Tm≦[mmmm]+65  (I);

and,(B) 1 to 50% by weight of a propylene homopolymer capable of forming aneutectic with a component (A) under a rapid cooling condition upon filmformation;

2. A polypropylenic resin composition of above 1 in which thecrystallization temperature (TcB ° C.) of a component (B) determined bya differential scanning calorimetry is higher by 0 to 40° C. than that(TcA ° C.) of a component (A);

3. A polypopylenic resin composition comprising (A′) 99 to 50% by weightof a propylenic polymer obtained by a polymerization using a metallocenecatalyst which is a propylene homopolymer and has an isotactic pentadfraction (mmmm) of 80 to 99%, an intrinsic viscosity [1] of 1.0 to 2.0dl/g and a molecular weight distribution (Mw/Mn ratio) of 3.5 or less,and, (B′) 1 to 50% by weight of a propylenic polymer obtained by apolymerization using a metallocene catalyst which is a propylenehomopolymer and has an intrinsic viscosity [η] of 0.01 to 1.0 dl/g and amolecular weight distribution (Mw/Mn ratio) of 3.5 or less; and,

4. A film formed using a propylenic polymer composition of any of above1 to 3.

VII. Seventh Invention

1. A propylenic resin comprising:

99 to 50% by weight of a propylene-α-olefin copolymer (A′) having thefollowing characteristics (a1) to (a5):(a1) the intrinsic viscosity [η] is 0.5 to 5.0 dl/g;(a2) the molecular weight distribution (Mw/Mn) is 3.5 or less;(a3) the stereoregularity index (P) is 50 to 99% by mole,(a4) it is a propylenic random copolymer produced by using propylene andethylene and/or an α-olefin having 4 to 20 carbon atoms, in which theethylene and/or an α-olefin having 4 to carbon atoms is contained in anamount of 0.1 to 30% by mole; and,(a5) the amount of the components which are dissolved out at 0° C. orlower in a temperature-raising fractional chromatography is 10% byweight or less;and,1 to 50% by weight or a propylenic polymer (B′) capable of forming aneutectic with a component (A′) under a rapid cooling condition upon filmformation;

2. A propylenic resin of above 1 in which the crystallizationtemperature (T′CB ° C.) of a component (B′) determined by a differentialscanning calorimetry is higher by 0 to 40° C. than that (T′CA ° C.) of acomponent (A′);

3. A propylenic resin comprising a copolymer (A) of propylene and anα-olefin having 5 or more carbon atoms and a propylenic polymer (B)having a crystallization temperature determined by a differentialscanning calorimetry which is higher than that of the component (A),wherein (A) is present in an amount of 55 to 99 parts by weight and (B)in an amount of 45 to 1 parts by weight;

4. A propylenic resin of above 1 in which the crystallizationtemperature (Tca ° C.) of a copolymer (A) and the crystallizationtemperature (Tcb ° C.) of a propylenic polymer (B), as determined by adifferential scanning calorimetry, are in the relationship representedby the following formula:

Tcb−Tca≧20  (1);

5. A propylenic resin of above 3 or 4 in which the propylenic resin,when subjected to a temperature-raising fractional chromatography,satisfies the following requirements (1), (2) and (3):

(1) when the main elution peak temperature is Tp (° C.), the amount ofthe components dissolved out within the temperature range from (Tp−5) °C. to (Tp+5) ° C. is 65% by weight or more;(2) the amount of the components dissolved out at 0° C. or lower is 3%by weight or less; and,(3) the amount of the components dissolved out at Tp+10° C. or higher is1 to 45% by weight, based on the total weight;

6. A propylenic resin of any of above 3 to 5 wherein the peak toptemperature on the side of the maximum temperature on thecrystallization curve of the propylenic resin, as determined by adifferential scanning calorimetry, is 85° C. or higher.

7. A propylenic resin of any of above 3 to 5 wherein the peak toptemperature on the side of the minimum temperature on the fusion curveof the propylenic resin, as determined by a differential scanningcalorimetry, is 150° C. or lower;

8. A propylenic resin of any of above 3 to 7 wherein a copolymer (A),when subjected to a temperature-raising fractional chromatography,satisfies the following requirements (A-1) and (A-2):

(A-1) when the main elution peak temperature is Tp, the amount of thecomponents dissolved out within the temperature range from (Tp−5) ° C.to (Tp+5) ° C. is 70 by weight or more; and,(A-2) the amount of the components dissolved out at 0° C. or lower is 3%by weight or less;

9. A propylenic resin of any of above 3 to 8 wherein a copolymer (A)satisfies at least one of the following requirements (A-3), (A-4) and(A-5):

(A-3) a copolymer (A) contains an α-olefin unit having 5 or more carbonatoms in an amount of 0.1 to 12% by mole;(A-4) the stereoregularity index (P) of a copolymer (A) is 85% by moleor higher; and,(A-5) a copolymer (A) has an intrinsic viscosity [η] determined in adecalin at 135° C. ranges from 0.5 to 3.0 dl/g;

10. A propylenic resin of any of above 3 to 9 wherein the α-olefin unithaving 5 or more carbon atoms which is a constituent unit of a copolymer(A) is at least one of 1-octene, 1-dodecene and 1-decene;

11. A film formed using a propylenic resin of any of above 1 to 10; and,

12. A laminated article comprising as at least one layer component apropylenic polymer of any of above 1 to 10.

VIII. Eighth Invention

1. A compound of a transition metal of Group 3 to Group or oflanthanoids in the periodic table represented by Formula (VIII):

wherein each of A³ and A⁴ denotes a crosslinking consisting of Group XIVmetal (C, Si, Ge, Sn) and may be same to or different from each other,X⁴ denotes a σ-binding or π-binding ligand, and when two or more X⁴ arepresent they may be same or different, Y⁵ is a Lewis base and when twoor more Y⁵ are present they may be same or different, and each Y⁵ may becrosslinked with other Y^(s) or X⁴, q is an integer of 1 to 5 andrepresents [(valency of M³)−2], r is an integer of 0 to 3, each of R²¹to R³⁰ denotes a hydrogen atom, a halogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group and aheteroatom-containing group, and M³ denotes a metal element of Group 3to Group 10 or of lanthanoids in the periodic table;

2. An olefin-polymerizing catalyst obtained by bringing (A) a transitionmetal element of Group 3 to Group 10 or of lanthanoids in the periodictable of above 1 into contact with (B) a compound capable of forming anionic complex by reacting with a transition metal compound as acomponent (A);

3. An olefin-polymerizing catalyst obtained by bringing (A) a transitionmetal element of Group 3 to Group 10 or of lanthanoids in the periodictable of above 1 into contact with (B) a compound capable of forming anionic complex by reacting with a transition metal compound as acomponent (A) and with (C) an organic aluminum compound;

4. A method for producing an olefinic polymer characterized in that anolefin is polymerized in the presence of an olefin-polymerizing catalystof above 2 or 3;

5. A method for producing an olefinic polymer of above 4 wherein anorganic aluminum compound is a trialkyl aluminum; and,

6. A method for producing an olefinic polymer of above 4 or 5 wherein anolefin is propylene.

BEST MODE FOR CARRYING OUT THE INVENTION

The embodiments of the first to eighth inventions are detailed below.

[I] First Invention

A propylenic polymer of the first invention consists of propylene aloneor propylene and ethylene and/or an α-olefin having 4 to 20 carbonatoms. An α-olefin having 4 to 20 carbon atoms includes ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene andthe like, and, in the invention, these may be employed alone or incombination with each other. A propylenic polymer of the invention ispreferably a propylene homopolymer.

Among propylenic polymers according to the invention, a propylenehomopolymer should have an isotactic pentad fraction (mmmm) within therange from 30 to 80%, preferably to 70%, more preferably 50 to 70%. Anisotactic pentad fraction less than 30% may cause an excessively reducedcrystallinity which may lead to a poor moldablity, while that exceeding80% may cause a loss of pliability, resulting in a problematic elevationof the heat seal temperature. A racemi-pentad fraction (rrrr) is aracemic moiety, represented in pentad as a unit, in a polypropylenemolecule chain. A value [rrrr/(1−mmmm)] can be obtained from a fractionin pentad described above, and serves as an index for the narrowness inthe regularity distribution of a propylene homopolymer. An increase inthis value is associated with a broader regularity distribution, andrepresents a mixture of a highly regular PP and APP such as aconventional polypropylene produced using an existing catalyst system,and thus is associated with an increased stickiness and a reducedtransparency. A value [rrrr/(1−mmmmm)] of a propylene homopolymer of theinvention which exceeds 0.1 causes a stickiness wherein theracemi-pentad fraction (rrrr) and the meso-pentad fraction (mmmm) arenot in percentage terms.

(2) Determination of pentad fraction and abnormal insertion Ameso-pentad fraction (mmmm) and a racemi-pentad fraction (rrrr) referredherein were obtained in accordance with the method proposed by A.Zambelli et al in Macromolecules, 6, 925 (1973) by determining themethyl signal in a ¹³C NMR spectrum and calculating an isotacticfraction and an atactic fraction, in a polypropylene molecule chain, asrepresented in pentad as a unit, as shown below.

<Calculation>

M=m/S×100

R=γ/S×100

S=Pββ+Pαβ+Pαγ

S:Signal intensity of side chain methyl carbon atom in all propyleneunits

Pββ:19.8 to 22.5 ppm Pαβ:18.0 to 17.5 ppm Pαγ:17.5 to 17.1 ppm

γ: Racemi-pentad chain: 20.7 to 20.3 ppmm: Meso-pentad chain: 21.7 to 22.5 ppm

With regard to (m−2, 1), (r−2, 1) and (1,3), the peaks in a ¹³C-NMRspectrum were assigned in accordance with the report by Grassi et al(Macromolecules, 21, p. 617 (1988)) and the report by Busico et al(Macromolecules, 27, p. 7538 (1994)) and the percentage of the contentinserted in each position was calculated based on the integratedintensity of each peak. A value (m−2, 1) was obtained by calculating theratio of the integrated intensity of a peak assigned to Pα, γ threoobserved near 17.2 ppm to the integrated intensity in all methyl carbonregion as a percentage of the content inserted in meso-2,1. A value(r−2, 1) was obtained by calculating the ratio of the integratedintensity of a peak assigned to Pα,γ threo observed near 15.0 ppm to theintegrated intensity in all methyl carbon region as a percentage of thecontent inserted in rasemi-2,1. A value (1, 3) was obtained bycalculating the ratio of the integrated intensity of a peak assigned toTβ,γ+observed near 31.0 ppm to the integrated intensity in all methinecarbon region as a percentage of the content inserted in 1, 3 position.When a peak to be assigned to a meso-2, 1 insertion, a racemi-2, 1insertion or a 1, 3 insertion could not be distinguished because of, forexample, being overlapped with noises, then each heterogeneous bindingcontent (m-2, 1), (r−2, 1) or (1, 3) was regarded as a zero value.

A ¹³C NMR spectrum was obtained using the following instruments underthe conditions specified below.

Instrument: Nippon Densi Model JNM-EX400 ¹³C-NMR deviceMethod: Proton complete decoupling methodConcentration: 220 mg/milliliterSolvent: A 90:10 solvent mixture (by volume) of 1,2,4-Trichlorobenzeneand benzene-d6

Temperature: 130° C. Pulse gap: 45°

Pulse interval: 4 secondsNumber of cycles: 10000 times

A comonomer unit content (mol %) in a propylenic polymer produced bycopolymerizing propylene and ethylene and/or an α-olefin having 4 to 20carbon atoms among the propylenic polymers according to the inventionwas obtained as described below. Thus, a ¹³C NMR spectrum was obtainedusing Nippon Densi Model JNM-EX400 ¹³C-NMR device under the conditionsspecified below and the calculation was made as described below.

Sample concentration: 220 mg/3 ml NMR solvent

NMR Solvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10 vol %)

Determination temperature: 130° C.

Pulse gap: 45°

Pulse interval: 10 secondsNumber of cycles: 4000 times

(a) Ethylene Unit

A random copolymer of propylene and ethylene, when subjected to ¹³C-NMR,exhibited the spectrum whose signals had the chemical shifts and theassignments indicated in the table shown below.

Assignments of Signals in ¹³C-NMR Spectrum of Ethylene-PropyleneCopolymer

Chemical Number shift Assignment 1 45.1-47.3 PPP Sαα 2 42.3 PPP Sαα 338.6 PPP Tαγ 4 38.  Sαγ 5 37.5 Sαδ 6 36.0 PPP Sαβ 7 36.0 PPP Tαβ 8 34.9EPP PEP Sαβ 9 34.6 EPP PEP Sαβ 10 34.1 EPP Tγγ 11 33.7 EEPP Tγδ 12 33.3EPE Tδδ 13 31.6 PPP Tβγ 14 31.4 EPP Tβγ 15 31.0 PPE Tβδ 16 30.7 PPP Sαβ17 30.5 PEEE Sγδ 18 30.0 EEE Sgg 19 29.0 EEE Tββ 20 27.3 PEE sβδ 21 24.6PEP sαβ 22 21.3-22.7 Pββ 23 20.6-21.3 Pββ 24 19.8-20.6 Pββ 25 17.6 Pαβ26 17.2 Pαγ NOTE) E represents an ethylene unit. NOTE) A chemical shiftis represented in ppm.

The ethylene unit content in the copolymer (α(% by mole)) was obtainedin accordance with the following equation (1) based on the spectrumdetermined by the ¹³C-NMR.

α=E/S×100  (1)

wherein S and E are each represented as follows:

S=IEPE+IPPE+IEEE+IPPP+IPEE+IPEP

E=IEEE+2/3(IPEE+IEPE)+1/3(IPPE+IPEP)

wherein:

IEPE=I(12) IPPE=I(15)+I(11)+(I(14)−I(11))/2+I(10) IEEP=I(18)/2+I(17)/4IPPP=I(19)+(I(6)+I(7))/2+I(3)+I(13)+I(11)+(I(14)−I(11))/2 IPEE=I(20)IPEP=(I(8)+I(9)−2×I(11))/4+I(21).

A isotactic triad fraction of a PPP chain was obtained as astereoregularity index (P (% by mole)) according to the equation (2)shown below.

P=Im/I×100  (2)

wherein Im and I are each represented as follows:

Im=I(22)

I=I(22)+I(23)+I(24)−{(I(8)+I(9))/2+I(10)+3/2×I(11)+I(12)+I(13)+I(15)}.

In the equation shown above, I(1), I(2) and the like represent theintensities of signal [1], signal [2] and the like, respectively.

Also a ¹³C NMR spectrum was obtained using Nippon Densi Model JNM-EX400NMR device under the conditions specified below and the calculation wasmade as described below.

Sample concentration: 220 mg/3 ml NMR solvent

NMR Solvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10 vol %)

Determination temperature: 130° C.

Pulse gap: 45°

Pulse interval: 10 secondsNumber of cycles: 4000 times

(a) 1-Butene Unit

The 1-butene unit content in the copolymer (a (% by mole)) was obtainedin accordance with the following equation based on the spectrumdetermined by the ¹³C-NMR.

$\alpha = {\frac{\left( {{{I(2)}/2} + {I(4)}} \right)}{\left\{ {{I(1)} + {I(2)} + {I(3)} + {I(4)} + {2 \times {I(9)}}} \right\}} \times 100}$

Also in accordance with the following equation, a stereoregularity index(P (% by mole)) of the copolymer was obtained.

$P = {\frac{\left( {I(12)} \right)}{\left\{ {{I(12)} + {I(13)} + {I(14)}} \right\}} \times 100}$

wherein (1), (2) and the like represent the signals of a spectrum of acopolymer of propylene and 1-butene determined by ¹³C-NMR. I(1), I(2)and the like represent the respective signal intensities. The signals ofa spectrum of a copolymer of propylene and 1-butene determined by¹³C-NMR are indicated in the table shown below.

Instead of the signal intensity of a P PP chain Sαβ carbon, the signalintensity of a PPP chain Sαβ carbon (signal intensity of (9)) wasindicated as an alternative.

Number Chemical shift Assignment 1 45.7-47.4 PP Sαα 2 43.0-44.9 PB Sαα 342.3 PPP Sαα 4 40.3 BB Sαα 5 36.6 PPP Tαγ 6 36.0 PPP Sαβ and PPP Sαβ 735.5 B unit Tββ 8 31.6 PPP Tβγ 9 30.6 PPP Sαβ 10 28.6-29.8 P unit Tββ 1127.8-28.4 B unit side chain methylene carbon 12 21.2-22.7 Pββ PPP(mm),PPB(mm), BPB(mm) 13 20.6-21.2 Pββ PPP(mr), PPB(mr), BPB(mr), PPB(rr),BPB(rr) 14 19.8-20.6 Pββ PPP(rr) 15 17.6 Pαβ 16 17.2 Pαγ 17 11.1 B unitside chain methyl carbon NOTE) B denotes a 1-butene unit.

A propylenic polymer produced by copolymerizing propylene and ethyleneand/or an α-olefin having 4 to 20 carbon atoms among propylenic polymersaccording to the invention should have a stereoregularity index (P)within the range from 55 to 90% by mole, preferably 65 to 80% by mole. Astereoregularity index (P) less than 55% may cause an excessivelyreduced crystallinity which may lead to a poor moldablity, while thatexceeding 90% may cause a loss of pliability, resulting in a problematicelevation of the heat seal temperature.

A propylenic polymer according to the invention has a molecular weightdistribution, defined as a ratio of a weight mean molecular weight Mw toa number mean molecular weight Mn, i.e., Mw/Mn, of 3.5 or less,preferably 3.0 to 2.0. A molecular weight distribution exceeding 3.5 istoo broad to achieve a sufficiently satisfactory physical properties.

An Mw/Mn defined above us a value calculated from the weight meanmolecular weight Mw and the number mean molecular weight Mn, as havingbeing converted to the values of polyethylene, by the determination by agel permeation chromatography (GPC) method using the followinginstruments under the conditions specified below.

GPC Instruments Column: TOSO GMHHR-H(S) HT

Detector: RI detector for liquid chromatography, WATERS 150

GPC Conditions Solvent: 1,2,4-Trichlorobenzene

Determination temperature: 145° C.Flow rate: 1.0 milliliter/minuteSample concentration: 2.2 mg/milliliterInjection volume: 160 microliterCalibration curve: Universal CalibrationAnalysis program: HT-GPC (Ver. 1.0)

A propylenic polymer according to the invention should have an intrinsicviscosity [η], determined in a decalin solvent at 135° C., of 0.8 to 5dl/g, preferably 1 to 3 dl/g, more preferably 1.5 to 2.5 dl/g. Anintrinsic viscosity [η] less than 0.8 dl/g may cause a stickiness, whilethat exceeding 5 dl/g may cause a reduced flowability which may lead toa poor moldability.

In a propylenic polymer composition according to the invention, apropylenic polymer preferably has a crystallization temperature (Tc(°C.)) and a melting point (Tm(° C.)) of the polymer, as determined by adifferential scanning calorimeter, which are in the relationshiprepresented by the following formula:

Tc≧0.75Tm−15.

A value of Tc less than 0.75Tm−15 may cause a higher tendency of a poormolding performance, due to which an inventive objective may notsuccessfully be achieved. For the purpose of a less tendency of suchpoor molding performance, a relationship represented by the followingformula:

Tc≧0.75Tm−10

is more preferred, and a relationship represented by the followingformula:

Tc≧0.75Tm−5

Is particularly preferred. The values of Tm and Tc were determined inaccordance with the method described in the examples.

While during an ordinary propylene polymerization process a 1,2insertion polymerization, which means that a carbon atom of a propylenemonomer on the side of a methylene undergoes a binding with an activecenter of a catalyst followed by a successive coordination of thepropylene monomers in the same manner whereby effecting thepolymerization, takes place generally, a 2,1 insertion or a 1,3insertion may also take place at a less incidence (sometimes referred toas abnormal insertion). In a homopolymer according to the invention, itis preferable that the incidence of such 2, 1 or 1,3 insertion is low.It is also preferable that these insertion rates satisfy therelationship represented by the following formula (1):

[(m−2,1)+(r−2,1)+(1,3)]≦5.0  (1)

wherein (m−2,1) is a % meso-2,1 insertion content determined by ¹³C-NMR,(r−2,1) is a % racemi-2,1 insertion content determined by ¹³C-NMR, and(1,3) is a % 1,3 insertion content determined by ¹³C-NMR, and, morepreferably, they satisfy the relationship represented by the followingformula (2):

[(m−2,1)+(r−2,1)+(1,3)]≦1.0  (2).

It is particularly preferred that they satisfy the relationshiprepresented by the following formula (3):

[(m−2,1)+(r−2,1)+(1,3)]≦0.1  (3).

When the relationship represented by Formula (1) is not satisfied, thecrystallinity is reduced far more than expected, and a stickiness mayarise. (m−2, 1), (r−2, 1) and (1,3) are the respective % insertioncontents obtained from the integrated intensities of the respectivepeaks after assigning the peaks in a ¹³C-NMR spectrum in accordance withthe report by Grassi et al (Macromolecules, 21, p. 617 (1988)) and thereport by Busico et al (Macromolecules, 27, p. 7538 (1994)). Thus, avalue (m−2, 1) was a % meso-2,1 insertion content calculated from theratio of the integrated intensity of a peak assigned to Pα,γ threoobserved near 17.2 ppm to the integrated intensity in all methyl carbonregion. A value (r−2, 1) was a % rasemi-2,1 insertion content calculatedfrom the ratio of the integrated intensity of a peak assigned to Pα,γthreo observed near 15.0 ppm to the integrated intensity in all methylcarbon region. A value (1, 3) was a % 1,3 insertion content calculatedfrom the ratio of the integrated intensity of a peak assigned toTβ,γ+observed near 31.0 ppm to the integrated intensity in all methinecarbon region.

A propylene homopolymer of the invention preferably exhibitssubstantially no peaks in a ¹³C-NMR spectrum which are assigned to amolecular chain terminal (n-butyl group) as a result of a 2,1 insertion.With regard to this molecular chain terminal as a result of a 2,1insertion, each % insertion content is calculated from the integratedintensity of each peak after assignment of the peak in the ¹³C-NMRspectrum in accordance with the report by Jungling et al (J. Polym.Sci.: Part A: Polym. Chem., 33, p 1305 (1995). In an isotacticpolypropylene, a peak appearing near 18.9 ppm is assigned to a terminalmethyl group carbon of an n-butyl group. The determination of a ¹³C-NMRfor an abnormal insertion or a molecular terminal may be performed usingthe instruments under the conditions described above.

In addition to the characteristics discussed above, the amount of aboiling diethylether extract, which is an index for a stickiness-causingcomponent level, of a propylenic polymer according to the invention ispreferably 0 to 10% by weight, more preferably 0 to 5% by weight, forthe purpose of preventing the bleeding out of a stickiness-causingcomponent on the surface of a molded article.

The amount of the components which are dissolved out at 25° C. or lowerin a temperature-raising fractionation (TREF), which is another indexfor a stickiness-causing component level is preferably 20 to 100% byweight because of the same reason, more preferably 0 to 10% by weight,and particularly 0 to 5% by weight. The TREF determination was performedby the method described in the examples.

A propylenic polymer produced by copolymerizing propylene and ethyleneand/or an α-olefin having 4 to 20 carbon atoms among propylenic polymersaccording to the invention is preferably a random copolymer. Thestructural unit derived from propylene exists preferably at a level of90% by mole or higher, more preferably 85% by mole or higher.

A propylenic polymer of the invention can be produced byhomopolymerizing propylene or copolymerizing propylene and ethyleneand/or an α-olefin having 4 to 20 carbon atoms in the presence of apolymerization catalyst comprising (A) a transition metal compoundrepresented by Formula (I):

and (B) a compound capable of forming an ionic complex by reacting witha transition metal compound as a component (A) or a derivative thereof.

In Formula (I) shown above, M denotes a metal element of Group 3 toGroup 10 or of lanthanoids in the periodic table, such as titanium,zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel,cobalt, palladium and lanthanoid metals, with titanium, zirconium andhafnium being preferred in view of their olefin polymerizationactivities. Each of E1 and E2 denotes a ligand selected from the groupconsisting of a substituted cyclopentadienyl group, indenyl group, asubstituted indenyl group, heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, amide group (—N<), phosphine group (—P<),a hydrocarbon group (>CR—, >C<) and a silicon-containing group(>SiR—, >Si<) (wherein R denotes hydrogen or a hydrocarbon group or aheteroatom-containing group having 1 to 20 carbon atom), and iscrosslinked with each other via A¹ and A². E¹ and E² may be same to ordifferent from each other. Preferred examples of E¹ and E² are asubstituted cyclopentadienyl group, indenyl group and a substitutedindenyl group.

X denotes a σ-binding ligand, and, when two or more Xs are present theymay be same or different, and each may be crosslinked with other X, E¹,E² or Y. Examples of X include a halogen atom, a hydrocarbon atom having1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, anarylalkoxy group having 6 to 20 carbon atoms, an amide group having 1 to20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms,a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, and thelike. A halogen atom may for example be a chlorine, fluorine, bromine oriodine atom. Examples of a hydrocarbon group having 1 to 20 carbon atomsare an alkyl group such as methyl, ethyl, propyl, butyl, hexyl,cyclohexyl, octyl groups and the like, an alkenyl group such as vinyl,propenyl, cyclohexenyl groups and the like; an arylalkyl group such asbenzyl, phenylethyl, phenylpropyl groups and the like; and an aryl groupsuch as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl,phenanthryl groups and the like. Among those listed above, an alkylgroup such as methyl, ethyl, propyl groups and the like and an arylgroup such as phenyl group are preferred. Examples of an alkoxy grouphaving 1 to 20 carbon atoms are an alkoxyl group such as methoxy,ethoxy, propoxy, butoxy groups and the like; and an aryloxy group suchas phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy groups and thelike. Examples of an arylalkoxy group having 6 to 20 carbon atoms arephenylmethoxy, phenylethoxy groups and the like. Examples of an amidegroup having 1 to 20 carbon atoms are an alkylamide group such asdimethylamide, diethylamide, dipropylamide, dibutylamide,dicyclohexylamide, methylethylamide groups and the like, an alkenylamidegroup such as divinylamide, dipropenylamide, dicyclohexenylamide groupsand the like; an arylalkylamide group such as dibenzylamide,phenylethylamide, phenylpropylamide groups and the like; and arylamidegroup such as diphenylamide, dinaphthylamide groups and the like.Examples of a silicon-containing group having 1 to 20 carbon atoms are amonohydrocarbon-substituted silyl group such as methylsilyl, phenylsilylgroups and the like; a dihydrocarbon-substituted silyl group such asdimethylsilyl, diphenylsilyl groups and the like; atrihydrocarbon-substituted silyl group such as trimethylsilyl,triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,dimethylphenylsilyl, methylphenyldisilyl, tritolylsilyl,trinaphthylsilyl groups and the like; a silyl ether group of ahydrocarbon-substituted silyl group such as trimethylsilylether group; asilicon-substituted alkyl group such as trimethylsilylmethyl group; anda silicon-substituted aryl group such as trimethylsilylphenyl group andthe like. Among those listed above, trimethylsilyl,phenethyldimethylsilyl groups are preferred. Examples of a sulfide grouphaving 1 to 20 carbon atoms are an alkylsulfide group such asmethylsulfide, ethylsulfide, propylsulfide, butylsulfide, hexylsulfide,cyclohexylsulfide, octylsulfide groups and the like and analkenylsulfide group such as vinylsulfide, propenyl sulfide,cyclohexenylsulfide groups and the like; an arylalkylsulfide group suchas benzylsulfide, phenylethylsulfide, phenylpropylsulfide groups and thelike; and an arylsulfide group such as phenylsulfide, tolylsulfide,dimethylsulfide, trimethylphenylsulfide, ethylphenylsulfide,propylphenylsulfide, biphenylsulfide, naphthylsulfide,methylnaphthylsulfide, anthracenylsulfide, phenanthnylsulfide groups andthe like. Examples of a sulfoxide group having 1 to 20 carbon atoms arean alkylsulfoxide group such as methylsulfoxide, methylsulfoxide,propylsulfoxide, butylsulfoxide, hexylsulfoxide, cyclohexylsulfoxide,octylsulfoxide groups and the like and an alkenylsulfoxide group such asvinylsulfoxide, propenylsulfoxide, cyclohexenylsulfoxide groups and thelike; an arylalkylsulfoxide group such as benzyl sulfoxide,phenylethylsulfoxide, phenylpropylsulfoxide groups and the like; and anarylsulfoxide such as phenylsulfoxide, tolylsulfoxide,dimethylphenylsulfoxide, trimethylphenylsulfoxide, ethylphenylsulfoxide,propylphenylsulfoxide, biphenylsulfoxide, naphthylsulfoxide,methylnaphthylsulfoxide, anthracenylsulfoxide, phenanthnylsulfoxidegroups and the like. Examples of an acyl group having 1 to 20 carbonatoms are an alkylacyl group such as formyl, acethyl, propionyl,butyryl, valeryl, palmitoyl, thearoyl, oleoyl groups and the like; anarylacyl group such as benzoyl, toluoyl, salicyloyl, cinnamoyl,naphthoyl, phthaloyl groups and the like; oxalyl, malonyl and succinylgroups derived from dicarboxylic acids such as oxalic acid, malonic acidand succinic acid, respectively, and the like. Y denotes a Lewis base,and, when two or more Ys are present they may be same or different, andeach may be crosslinked with other Y, E¹, E² or X. Examples of the Lewisbase represented by said Y are amines, ethers, phosphines, thioethersand the like. The amines may for example be an amine having 1 to 20carbon atoms, and typically an alkylamine such as methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine,dimethylamine, diethylamine, dipropylamine, dibutylamine,dicyclohexylamine, methylethylamine and the like and an alkenylaminesuch as vinylamine, propenylamine, cyclohexenylamine, divinylamine,dipropenylaine, dicyclohexenylamine and the like; an arylalkylamine suchas phenylamine, phenylethylamine, phenylpropylamine and the like; andarylamine such as diphenylanine, dinaphthylamine and the like. Ethersmay for example be an aliphatic monoether compound such as methylether,ethylether, propylether, isopropylether, butylether, isobutylether,n-amylether, isoamylether and the like; an aliphatic mixed ethercompound such as methylethylether, methylpropylether,methylisopropylether, methyl-n-amylether, methylisoamylether,ethylpropylether, ethylisopropylether, ethylbutylether,ethyliobutylether, ethyl-n-amylether, ethylisoamylether and the like; analiphatic unsaturated ether compound such as vinylether, allylether,methylvinylether, methylallylether, ethylvinylether, ethylallylether andthe like; an aromatic ether compound such as anisol, phenethol,phenylether, benzylether, phenylbenzylether, α-naphthylether,β-naphthylether and the like, as well as a cyclic ether compound such asethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran,tetrahydropyrane, dioxane and the like. An example of the phosphines maybe a phosphine having 1 to 20 carbon atoms. Those included typically arean alkylphosphine including a monohydrocarbon-substituted phosphine suchas methylphosphine, ethylphosphine, propylphosphine, butylphosphine,hexylphosphine, cyclohexylphosphine, octylphosphine and the like; adihydrocarbon-substituted phosphine such as dimethylphosphine,diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine,dicyclohexylphosphine, dioctylphosphine and the like; atrihydrocarbon-substituted phosphine such as dimethylphosphine,triethylphosphine, tripropylphosphine, tributylphosphine,trihexylphosphine, tricyclohexylphosphine, trioctylphosphine and thelike and a monoalkenylphosphine such as vinylphosphine,propenylphosphine, cyclohexenylphosphine and the like as well as adialkenyl phosphine whose hydrogen atoms on the phosphorus were replacedwith two alkenyl groups; a trialkenyl phosphine whose hydrogen atoms onthe phosphorus were replaced with three alkenyl groups; anarylalkylphosphine such as benzylphosphine, phenylethylphosphine,phenylpropylphosphine and the like; a diarylalkyl phosphine or anaryldialkylphosphine whose hydrogen atoms on the phosphorus werereplaced with three aryl or alkenyl groups; phenylphosphine,tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine,ethylphenylphosphine, propylphenylphosphine, biphenylphosphine,naphthylphosphine, methylnaphthylphosphine, anthracenylphosphine,phenanthracenyl phosphine; a di(alkylaryl)phosphine whose hydrogen atomson the phosphorus were replaced with 2 aklkylaryl groups; atri(alkylaryl)phosphine whose hydrogen atoms on the phosphorus werereplaced with 3 aklkylaryl groups, and the like. An example of thethioethers may be a sulfide mentioned above.

Each of A¹ and A² denotes a divalent crosslinking group having twoligands, including a hydrocarbon group having 1 to carbon atoms, ahalogen-containing hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing group, a germanium-containing group, a tin-containinggroup, —O—, —CO—, —S—, —SO—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR—wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1to 20 carbon atoms, and each may be same to or different from eachother. Among such crosslinking groups, at least one is a crosslinkinggroup consisting of a hydrocarbon group having one or more carbon atoms.An example of such crosslinking group is one represented by Formula:

wherein B denotes an element of Group XIV in the periodic table such ascarbon, silicon, germanium and tin; and each of R1 and R2 denotes ahydrogen atom or a hydrocarbon group having 1 to carbon atoms, and maybe same to or different from each other, or alternatively may bind toeach other to form a cyclic structure; and e denotes an integer of 1 to4, and may typically be methylene, ethylene, ethylidene, propylidene,isopropylidene, cyclohexylidene, 1,2-cyclohexylene, vinylidene (CH2═C═),dimethylsilylene, diphenylsilylene, methylphenylsilylene,dimethylgermylene, dimethylstannylene, tetramethyldisilylene,diphenyldisilylene groups and the like. Among those listed above,ethylene, isopropylidene and dimethylsilylene groups are preferred. q isan integer of 1 to 5 and represents [(valency of M)−2], and r is aninteger of 0 to 3.

In a transient metal compound represented by Formula (I), when E¹ and E²are substituted cyclopentadienyl group, indenyl group or substitutedindenyl group, then the crosslinking groups of A¹ and A² are preferablyin the forms of a (1,2′) (2,1′) double crosslinking.

Among the transient metal compounds represented by Formula (I), oneemployed preferably is a transient metal compound having, as a ligand, abiscyclopentadienyl derivative in a double crosslinking form such asthose represented by Formula (II):

In Formula (II) shown above, M, A¹, A², q and r are defined as describedabove. X¹ denotes a σ-binding ligand, and, when two or more X¹s arepresent they may be same or different, and each may be crosslinked withother X¹ or Y². Such X¹ may for example be one exemplified in thedescription of X in Formula (I). Y¹ denotes a Lewis base, and, when twoor more Y¹s are present they may be same or different, and each may becrosslinked with other Y¹ or X¹. Such Y¹ may for example be oneexemplified in the description of Y in Formula (I). Each of R³ to R⁸denotes a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group or a heteroatom-containinggroup, provided that at least one of them is not a hydrogen atom. Eachof R³ to R⁸ may be same to or different from each other, and anyadjacent two of them may be taken together to form a ring.

This transient metal compound having as a ligand a biscyclopentadienylderivative in a double crosslinking form has the ligand in the forms ofa (1,2′) (2,1′) double crosslinking.

Examples of a transient metal compound represented by Formula (I) are(1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)zirconium dichloride,(1,2′-methylene)(2,1′-methylene)-bis(indenyl)zirconium dichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,5-benzoindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,7-diisopropylindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(4-phenylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methyl-4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-benzoindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-ethylene)-bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-I-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-phenylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4,5-benzoindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4,7-di-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4-phenylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-methyl-4-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(5,6-benzoindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-i-propylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(3-phenylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-i-propylindenyl)zirconiumdichloride, (1,2′dimethylsilylene)(2,1′-methylene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(indenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-methylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-i-propylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)-bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconium dichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconium dichloride,(1,2′-ethylene)(2,1′-methylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconium dichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)(3-methylcyclopentadienyl)(3′-methylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-isopropylcyclopentadienyl)(3′-methyl-5′-isopropylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-ethylcyclopentadienyl)(3′-methyl-5′-ethylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-n-butylcyclopentadienyl)(3′-methyl-5′-n-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)(3-methyl-5-phenylcyclopentadienyl)(3′-methyl-5′-phenylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)(3-methyl-5-i-propylcyclopentadienyl)(3′-methyl-5′-i-propylcyclopentadienyl)zirconiumdichloride and the like as well as the compounds obtained by replacingzirconium in the compounds listed above with titanium or hafnium. It isa matter of course that the compounds listed above are non-limitingexamples. Analogous compounds of other groups or of lanthanoids may alsobe employed.

While a component (B-1) among the components (B) may be any ioniccompound capable of forming an ionic complex by reacting with atransition metal compound as a component (A), compounds represented byFormulae (III), (IV):

([L¹-R⁹]^(K+))_(a)([Z]⁻)_(b)  (III)

([L²]^(K+))_(a)([Z]⁻)_(b)  (IV)

wherein L² denotes M², R¹⁰R¹¹M³, R¹² ₃C or R¹³M³,wherein L¹ denotes a Lewis base, [Z]⁻ denotes a non-coordinating anion[Z¹]⁻ and [Z²]⁻, wherein [Z¹]⁻ denotes an anion in which two or moregroups are bound to an element, i.e., [M¹G¹G² . . . G^(f)]⁻, wherein M¹is an element of Groups VI to XVI in the periodic table, preferably ofGroups XIII to XVI in the periodic table; each of G¹ to G^(f) denotes ahalogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylaminogroup having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbonatoms, an aryl group having 6 to 20 carbon atoms, an arylalkoxy grouphaving 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbonatoms, an arylalkyl group having 7 to 40 carbon atoms, ahalogen-substituted hydrocarbon group having 1 to 20 carbon atoms, anacyloxy group having 1 to 20 carbon atoms, an organic metalloid group ora heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms;two or more of G¹ to G^(f) may be taken together to form a ring; fdenotes an integer represented by [(valency of center metal M¹)+1],[Z²]⁻ denotes a conjugate base of a Brφnsted acid alone or a combinationof a Brφnsted acid and a Lewis acid whose logarithmic number of areciprocal number of an acid dissociation constant (pK(a) is −10 orless, or a conjugate base of one generally referred to be a super acid;a Lewis base may be coordinated; R⁹ denotes a hydrogen atom, an alkylgroup having 1 to 20 carbon atoms, an aryl, alkylaryl or arylalkyl grouphaving 6 to 20 carbon atoms, each of R¹⁰ and R¹¹ is a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group or afluorenyl group, R¹² denotes an alkyl, aryl, alkylaryl or arylalkylgroup having 1 to 20 carbon atoms; R¹³ denotes a large cyclic ligandsuch as tetraphenylporphyrin, phthalocyanine and the like; k denotes aninteger of 1 to 3 which is an ionic valency of [L¹-R⁹], [L²], a denotesan integer of 1 or more, b=(k×a); M² comprises an element of Groups I toIII, XI to XIII, XVII in the periodic table, and M² denotes an elementof Groups VII to XII are employed preferably.

Examples of L1 are amines including ammonia, methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,N,N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine,methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline,p-nitro-N,N-dimethylaniline and the like, phosphines such astriethylphosphine, triphenylphosphine, diphenylphosphine and the like,thioethers such as tetrahydrothiophene, esters such as ethyl benzoate,nitriles such as acetonitrile, benzonitrile and the like.

R⁹ may for example be methyl, ethyl, benzyl, trityl groups and the like,R¹⁰ and R¹¹ may for example be cyclopentadienyl, methylcyclopentadienyl,ethylcyclopentadienyl, pentamethylcyclopentadienyl groups and the like.R¹² may for example be phenyl, p-tolyl, p-methoxyphenyl groups and thelike, while R¹³ may for example be tetraphenylporphine, phthalocyanine,allyl, methallyl groups and the like. M² may for example be Li, Na, K,Ag, Cu, Br, I, I, and the like, while M³ may for example be Mn, Fe, Co,Ni, Zn and the like.

In [Z¹]⁻, i.e. in [M¹G¹G² . . . G^(f)]⁻, M¹ may for example be B, Al,Si, P, As, Sb, preferably B and Al. G¹, G² to G^(f) may for example be adialkylamino group such as dimethylamino, diethylamino groups and thelike, an alkoxy group or an arylalkoxy group such as methoxy, ethoxy,n-butoxy, phenoxy groups and the like, a hydrocarbon group such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl,n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenylgroups and the like, a halogen atom such as fluorine, chlorine, bromineand iodine, a heteroatom-containing hydrocarbon group such asp-fluorphenyl, 3,5-difluorophenyl, pentachlorophenyl,3,4,5-trifluorophenyl, pentafluorophenyl,3,5-bis(trifluoromethyl)phenyl, bis(trimethylsilyl)methyl groups and thelike, an organic metalloid group such as pentamethylantimony,trimethylsilyl, trimethylgermyl, diphenylarsine, dicyclohexylantimonygroups and diphenylboron and the like.

A non-coordinating anion, i.e., [Z²]⁻ which is a conjugate base of aBrφnsted acid alone or a combination of a Brφnsted acid and a Lewis acidwhose pKa is −10 or less, may for example be, trifluoromethanesulfonateanion (CF₃SO₃)⁻, bis(trifluoromethanesulfonyl)methyl anione,bis(trifluoromethanesulfonyl)benzyl anione,bis(triphenylmethanesulfonyl)amide, perchlorite anion (ClO₄)⁻,trifluoroacetate anion (CF₃ CO₂)⁻, hexafluoroantimony anion (SbF₆)⁻,fluorosulfonate anione/pentafluoroantimony (FSO₃/SbF₅)⁻, fluorosulfonateanion/pentafluoroarsenic (FSO₃/AsF₅)⁻,trifluoromethanesulfonate/pentafluoroantimony (CF₃SO₃/SbF₅)⁻ and thelike.

Examples of an ionic compound capable of forming an ionic complex byreacting with a transition metal compound as a component (A), i.e.,examples of a compound as a component (B-1) are triethylammoniumtetraphenylborate, tri-n-butylammonium tetraphenylborate,trimethylammonium tetraphenylborate, tetraethylammoniumtetraphenylborate, methyl(tri-b-butyl)ammonium tetraphenylborate,benzyl(tri-b-butyl)ammonium tetraphenylborate, dimethylphenylammoniumtetraphenylborate, triphenyl(methyl)ammonium tetraphenylborate,trimethylanilinium tetraphenylborate, methylpyridiniumtetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium)tetraphenylborate, triethylammoniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetra-n-butylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, benzyl(tri-n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, triphenyl(methyl)ammoniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylaniliniumtetrakis(pentafluorophenyl)borate, methylpyridiniumtetrakis(pentafluorophenyl)borate, benzylpyridiniumtetrakis(pentafluorophenyl)borate,methyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate,benzyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate,methyl(4-cyanopyridinium)tetrakis(pentafluorophenyl)borate,triphenylphosphonium tetrakis(pentafluorophenyl)borate,dimethylanilinium tetrakis[bis(3,5-ditrifluoromethyl)phenyl]borate,ferrocenium tetraphenylborate, silver tetraphenylborate, trityltetraphenylborate, tetraphenylporphyrinmanganese tetraphenylborate,ferrocenium tetrakis(pentafluorophenyl),(1,1′-dimethylferrocenium)tetrakis(pentafluorophenyl)borate,decamethylferrocenium tetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, theoraphenylporphyrinmanganesetetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silverhexafluorophosphate, silver hexafluoroarsenate, silver perchlorite,silver trifluoroacetate, silver trifluoromethanesulfonate, and the like.

Only one of or a mixture of two or more of the components (B-1), eachcapable of forming an ionic complex by reacting with a transition metalcompound as a component (A), may be employed. A component (B-2) which isan aluminoxane may for example be a linear aluminoxane represented byFormula (V):

wherein R¹⁴ is a hydrocarbon group such as an alkyl, alkenyl, aryl,arylalkyl groups having 1 to 20, preferably 1 to 12 carbon atoms or is ahalogen atom, w represents a degree of polymerization which is usuallyan integer of 2 to 50, preferably 2 to 40; each R¹⁴ may be same to ordifferent from each other, and also may be a cyclic aluminoxanerepresented by Formula (VI):

wherein R¹⁴ and w are defined as in Formula (V) shown above.

In a method for producing an aluminoxane described above, analkylaluminium is brought into contact with a condensing agent such aswater, while no particular procedure therefor is specified and thereaction may be in accordance with a known method. For example, [1] amethod in which an organic aluminum compound is dissolved in an organicsolvent and then brought into contact with water, [2] a method in whichan organic aluminum compound is added upon a polymerization and water issubsequently added, [3] a method in which a water of crystallizationassociated with a metal or a water adsorbed onto an inorganic or organicsubstance is reacted with an aluminum compound, and [4] a method inwhich a tetraalkyldialuminoxane is reacted with a trialkylaluminium andthen with water may be employed. A toluene-insoluble aluminoxane mayalso be employed.

Only one aluminoxane may be employed, and a combination of two or moremay also be employed.

The molar ratio of a catalyst component (A) to a catalyst component (B)when employing a compound (B-1) as a catalyst component (B) ispreferably 10:1 to 1:100, more preferably 2:1 to 1:10, and a ratiodeparting from this range is not advantageous industrially because of anincreased catalyst cost per unit weight of a polymer. When a compound(B-2) is employed, the molar ratio is preferably 1:1 to 1:1000000, morepreferably 1:10 to 1:10000, and particularly 1:10 to 1:1000. A ratiodeparting from this range is not advantageous industrially because of anincreased catalyst cost per unit weight of a polymer. As a catalystcompound (B), a component (B-1) or (B-2) may be employed alone or incombination of two or more such components.

A polymerization catalyst employed in a production method according tothe invention may comprise as a component C an organic aluminum compoundin addition to components (A) and (B) described above.

As an organic aluminum compound as a component C may be a compoundrepresented by Formula (VII):

R¹⁵ _(v)AlJ_(3-v)  (VII)

Wherein R15 denotes an alkyl group having 1 to 10 carbon atoms, Jdenotes a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, anaryl group having. 6 to 20 carbon atoms or a halogen atom, and v is aninteger of 1 to 3.

Examples of a compound represented by Formula (VII) shown above aretrimethylaluminium, triethylaluminium, triisopropylaluminium,triisobutylaluminium, dimethylaluminium chloride, diethylaluminiumchloride, methylaluminium dichloride, ethyl aluminium dichloride,dimethylaluminium fluoride, diisobutylaluminium hydride,diethylaluminium hydride, ethylaluminium sesquichloride and the like.Among those listed above, trimethylaluminium, triethylaluminium andtriisobutylaluminium are preferred, and triisobutylaluminium is morepreferred.

Only one organic aluminum compound listed above may be employed or acombination of two or more such compound may be employed.

The molar ratio of a catalyst component (A) to a catalyst component (C)is preferably 1:1 to 1:10000, more preferably 1:5 to 1:2000, mostpreferably 1:10 to 1:1000. While a catalyst component (C) serves toimprove the polymerization activity per unit quantity of a transitionmetal, it remains uselessly and disadvantageously in the polymer as alarge amount of surplus of the organic aluminum compound when employedin an excessive amount.

In a production method according to the invention, components (A), (B)and (C) may be subjected to a preliminary contact.

Such preliminary contact may for example be effected by bringing acomponent (B) into contact with a component (A) by any known method.This preliminary contact serves to improve the catalyst activity andallows the amount of a component (B) to be reduced, thus being effectivein reducing the catalyst cost. In addition to the effectivenessdescribed above, an improvement with regard to the molecular weight canbe obtained by bringing a component (A) into contact with a component(B-2).

The temperature at which a preliminary contact is effected rangesusually from −20° C. to 200° C., preferably −10° C. to 150° C., morepreferably 0° C. to 80° C. In such preliminary contact, a solvent whichcan be employed includes inert hydrocarbons and aliphatic hydrocarbons.Among these, an aromatic hydrocarbon is particularly preferred.

In the present invention, at least one of the catalyst components may beemployed as being supported on a suitable carrier. While the materialfor such carrier is not particularly limited and may be any of inorganicoxide carriers and other inorganic and organic carriers, an inorganicoxide carrier or other inorganic carriers are particularly preferred.

An inorganic oxide carrier may for example be SiO₂, Al₂O₃, MgO, ZrO₂,TiO₂, Fe₂O₃, B₂O₃, CaO, ZnO, BaO, ThO₂, as well as mixtures thereof suchas silica alumina, zeolite, ferrite, glass fibers, carbons and the like.Among those listed above, SiO₂ and Al₂O₃ are particularly preferred. Theinorganic oxide carriers listed above may contain small amounts ofcarbonates, nitrates, sulfates and the like.

Other carriers than those described above may for example be a magnesiumcompound represented by Formula MgR¹⁶xX¹y, such as MgC₁₂, Mg(OC₂H₅)₂ andthe like, as well as complex salts thereof. In this formula, R¹⁶ denotesan alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X¹ denotesa halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to2, y is 0 to 2, and x+Y=2. Each R¹⁶ may be same or different, as may beeach X¹.

An organic carrier may for example be a polymer such as polystyrene, astyrene-divinylbenzene copolymer, polyethylene, propropylene, asubstituted polystyrene, polyallylate and the like, as well as a starch.

One employed preferably as a carrier in the invention is MgCl₂,MgCl(OC₂H₅), Mg(OC₂H₅)₂, SiO₂, Al₂O₃ and the like. While the state of acarrier may vary dependent of the type and the production methodthereof, a mean particle size is usually 1 to 300 μm, preferably 10 to200 μm, more preferably 20 to 100 μm.

A smaller particle size may result in an increase in microparticles inthe polymer, while a larger particle size may result in an increase incoarse particles in the polymer, which leads to a reduced bulk densityor a plugging in a hopper.

The specific surface area of a carrier is usually 1 to 1000 m²/g,preferably 50 to 500 m²/g, and the micropore void volume is usually 0.1to 5 cm³, preferably 0.3 to 3 cm³/g.

When either of the specific surface area or the micropore void volumedeparts from the range specified above, the catalyst activity may bereduced. The specific surface area and the micropore void volume can forexample be calculated based on the volume of the nitrogen gas adsorbedin accordance with BET method (See Journal of the American ChemicalSociety, Vol. 60, page 309 (1983)).

A carrier listed above is used appropriately after being sinteredusually at 100 to 1000° C., preferably 150 to 800° C.

When at least one of the catalyst components is supported on a carrierlisted above, at least one of catalyst components (A) and (B),preferably both of catalyst components (A) and (B) are supported.

A method for allowing at least one of a component (A) and a component(B) to be supported is not particularly limited, and those which may beexemplified are [1] a method in which at least one of a component (A)and a component (B) is mixed with a carrier, [2] a method in which acarrier is treated with an organic aluminum compound or ahalogen-containing silicon compound and then mixed with at least one ofa component (A) and a component (B) in an inert solvent, [3] a method inwhich a carrier is admixed with a component (A) and/or a component (B)together with an organic aluminum compound or a halogen-containingsilicon compound, [4] a method in which a component (A) or a component(B) is supported on a carrier ant then mixed with a component (B) or acomponent (A), [5] a method in which a contact reaction product betweena component (A) and a component (B) is mixed with a carrier, and [6] amethod in which a contact reaction between a component (A) and acomponent (B) is effected in the presence of a carrier.

In the methods [4], [5] and [6] described above, an organic aluminumcompound as a component (C) may be added.

A catalyst thus obtained may be used in a polymerization after beingisolated as a solid by distilling a solvent off, or alternatively it maybe subjected directly to a polymerization.

In the invention, a catalyst may be produced also by allowing at leastone of a component (A) and a component (B) to be supported on a carrierwithin the system of polymerization. For example, at least one of acomponent (A) and a component (B) is admixed with a carrier, ifnecessary together with an organic aluminum compound as a component (C)described above, and then an olefin such as ethylene was subjected to apreliminary polymerization for 1 minutes to 2 hours at −20° C. to 200°C. under an atmospheric pressure to 20 kg/cm² to produce a catalystparticle.

In the invention, the weight ratio of a component (B-1) to a carrier ispreferably 1:5 to 1:10000, more preferably 1:10 to 1:500, while theweight ratio of a component (B-2) to a carrier is preferably 1:0.5 to1:1000, more preferably 1:1 to 1:50. When a mixture of two or morecomponents (B) are employed, it is preferred that the weight ratio ofeach component (B) to a carrier is in the range specified above. Theweight ratio of a component (A) to a carrier is preferably 1:5 to1:10000, more preferably 1:10 to 1:500.

When the ratio of a component (B) [component (B-1) or component (B-2)]to a carrier or the ratio of a component (A) to a carrier is departingfrom the ranges specified above, the activity may be reduced. Thepolymerization catalyst of the invention thus prepared usually has amean particle size of 2 to 200 μm, preferably 10 to 150 μm, particularly20 to 100 μm, and a specific surface area usually of 20 to 1000 m²/g,preferably 50 to 500 m²/g. A mean particle size less than 2 μm mayresult in an increase in microparticles in the polymer, while thatexceeding 200 μm may result in an increase in coarse particles in thepolymer. A specific surface area less than 20 m²/g may result in areduced activity, while that exceeding 100 m²/g may result in a reducedbulk density of the polymer. In an inventive catalyst, the amount of atransition metal in 100 g of a carrier is usually 0.05 to 10 g,preferably 0.1 to 2 g. An amount of a transition metal departing fromthe range described above may result in a reduced activity.

By means of employing a carrier as a support as described above, apolymer having industrially advantageous high bulk density and excellentparticle size distribution can be obtained.

In a production method according to the present invention, apolymerization catalyst described above is employed to homopolymerizepropylene, or copolymerize propylene and ethylene and/or an α-olefinhaving 4 to 20 carbon atoms.

While a polymerization method is not particularly limited in theinvention and may be a slurry polymerization, a vapor phasepolymerization, a bulk polymerization, a solution polymerization, asuspension polymerization and the like, those particularly preferred area slurry polymerization and a vapor phase polymerization.

A polymerization condition involves a polymerization temperature usuallyof −100 to 250° C., preferably −50 to 200° C., more preferably 0 to 130°C. The ratio of a catalyst to a reactant, represented as startingmonomer/component (A) (molar ratio), is preferably 1 to 10⁸,particularly 100 to 10⁵. A polymerization time usually of 5 minutes orlonger, and a reaction pressure preferably of atmospheric pressure to200 kg/cm²G, particularly atmospheric pressure to 100 kg/cm²G areemployed.

The molecular weight of a polymer may be adjusted by appropriatelyselecting the types of respective catalyst components, the amounts andthe polymerization temperature, or by performing a polymerization in thepresence of hydrogen.

When a polymerization solvent is used, it may for example be an aromatichydrocarbon such as benzene, toluene, xylene, ethylbenzene and the like,an alicyclic hydrocarbon such as cyclopentane, cyclohexane,methylcyclohexane and the like, an aliphatic hydrocarbon such aspentane, hexane, heptane, octane and the like, a halogenated hydrocarbonsuch as chloroform, dichloromethane and the like. Only one of thesesolvents may be employed, or a combination of two or more may beemployed. A monomer such as an α-olefin may also be employed as asolvent. A certain polymerization procedure may need no use of asolvent.

Upon polymerization, a polymerization catalyst described above may beused to perform a preliminary polymerization. While a preliminarypolymerization may for example be conducted by bringing a small amountof an olefin into contact with a solid catalyst component, the procedurefor such contact is not particularly limited and may be any knownprocedure. An olefin employed in a preliminary polymerization is notparticularly limited, and may be any of those listed above, such asethylene, an α-olefin having 3 to carbon atoms, or a mixture thereof,while it is advantageous to use an olefin similar to that employed in amain polymerization.

A preliminary polymerization may be performed usually at −20 to 200° C.,preferably −10 to 130° C., more preferably 0 to 80° C. A solvent whichmay be used in a preliminary polymerization is an inert hydrocarbon, analiphatic hydrocarbon, an aromatic hydrocarbon, a monomer and the like.Among these, an aliphatic hydrocarbon is particularly preferred. Apreliminary polymerization may be performed without using any solvent.

The conditions of a preliminary polymerization may preferably beadjusted so that the intrinsic viscosity [η] (determined in a decalin at135° C.) is 0.2 dL/g or higher, particularly 0.5 dl/g or higher and theamount of a preliminary polymerization product per 1 millimole of atransition metal component in a catalyst ranges from 1 to 10000 g,particularly to 1000 g.

A propylenic polymer according to the invention thus obtained can beformed into a molded article by a press molding. It may be used also asa modifier for imparting a resin with a pliability.

A propylenic polymer composition according to the invention is obtainedby admixing a propylene homopolymer described above [component (a)] or apropylenic polymer produced by copolymerizing a propylene and ethyleneand/or an α-olefin having 4 to 20 carbon described above [component(a′)]with a nucleating agent (b) at a level of 10 ppm or higher.

A nucleating agent as a component. (b) may be any of those capable ofinducing a crystalline nucleation rapidly and lowering the supercoolingdegree required for initiating a crystallization without affecting thephysical properties of a propylenic polymer adversely.

Examples of a nucleating agent used in the invention are a high meltingpolymer, an organic carboxylic acid or its metal salt, an aromaticsulfonate or its metal salt, an organic phosphorus compound or its metalsalt, a dibenzylidene sorbitol or its derivative, a rosinic acid partialmetal salt, an inorganic microparticle, imides, amides, quinacridones,quinones as well as mixtures thereof.

A high melting polymer may for example be a polyolefin such aspolyethylene and polypropylene, a polyvinylcycloalkane such aspolyvinylcyclohexane and polyvinylcyclopentane, as well as poly3-methylpentene-1, poly 3-methylbutene-1, polyalkenylsilanes and thelike. A metal salt may for example be aluminum benzoate, aluminump-t-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, sodiumpyrrole carboxylate and the like. A dibenzylidene sorbitol and itsderivative may for example be dibenzylidene sorbitol,1,3:2,4-bis(o-3,4-dimethylbenzylidene)sorbitol,1,3:2,4-bis(o-2,4-dimethylbenzylidene)sorbitol,1,3:2,4-bis(o-4-ethylbenzylidene)sorbitol,1,3:2,4-bis(o-4-chlorobenzylidene)sorbitol, 1,3:2,4-dibenzylidenesorbitol and the like. Typically, GELOL MD or GELOL MD-R (trade names)available from SHINNIPPON RIKA (KK) may also be exemplified.

A rosinic acid partial metal salt may for example be PINECRYSTAL KM1600,PINECRYSTAL KM1500, PINECRYSTAL KM1300 (trade names) and the like whichare available from ARAKAWA KAGAKU KOGYO (KK).

An inorganic microparticle may for example be talc, clay, mica,asbestos, glass fiber, glass flake, glass bead, calcium silicate,montmorillonite, bentonite, graphite, aluminium powder, alumina, silica,kieselguhr, titanium oxide, magnesium oxide, pumice powder, pumiceballoon, aluminum hydroxide, magnesium hydroxide, basic magnesiumcarbonate, dolomite, calcium sulfate, potassium titanate, bariumsulfate, calcium sulfite, molybdenum sulfite and the like. Among thesesubstances, an organic metal phosphate represented by Formula (VIII) andan inorganic microparticle such as talc are preferable when an inventivepropylenic polymer composition is applied to a food product because oftheir reduced odor generation.

wherein R¹⁷ denotes a hydrogen atom or an alkyl group having 1 to 4carbon atoms, each of R¹⁸ and R¹⁹ denotes a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, cycloalkyl, aryl or aralkyl group; Mdenotes an alkaline metal, an alkaline earth metal, aluminum or zinc,and in case that M is an alkaline metal then m is 0 and n is 1, and incase that M is a divalent metal then n is 1 or 2 and m is 1 when n is 1and m is 0 when n is 2, and in case that M is aluminium then m is 1 andn is 2.

In addition, since a film formed by molding a propylenic polymercomposition containing an inorganic microparticle such as talc also hasan excellent slipperiness, it gives an improvement in a secondaryprocessing performance such as bag making or printing performance, dueto which it is suitable as a general-purpose packaging film subjected toa high speed bag making machine including various automaticfilling-packaging laminators.

A film produced by molding a propylenic polymer composition containing adibenzylidene sorbitol or its derivative as a nucleating agent has aparticularly excellent transparency which is highly display-oriented,and which makes it to be suitable as a package film of a toy or astationery.

Examples of a dibenzylidene sorbitol are1,3:2,4-bis(o-3,4-dimethylbenzylidene)sorbitol,1,3:2,4-bis(o-2,4-dimethylbenzylidene)sorbitol,1,3:2,4-bis(o-4-ethylbenzylidene)sorbitol,1,3:2,4-bis(o-4-chlorobenzylidene)sorbitol, 1,3:2,4-dibenzylidenesorbitol and the like.

A film produced by molding a propylenic polymer composition containingan amide compound as a nucleating agent has a particularly excellentrigidity and a less problematic wrinkling when being wound during a highspeed bag making, due to which it is suitable as a general-purposepackaging film subjected to a high speed bag making machine.

An amide compound may for example be dianilide adipate, dianilidesuberate and the like.

The amount of an nucleating agent added is usually 10 ppm or higher,preferably 50 to 3000 ppm based on a propylenic copolymer. An amountless than 10 ppm does not improve a low temperature heat sealperformance, while an increase in a nucleating agent may fail to exhibita corresponding increase in the effect.

In view of the transparency and the impact resistance of a propylenicpolymer composition, the amount of a nucleating agent to be added is1000 ppm or less, particularly 500 ppm or less, although it may varydepending on the type of the nucleating agent. Typically wen asorbitol-based nucleating agent is employed, dibenzylidene sorbitol, inthis case, is added at 3000 ppm or less, more preferably 1500 ppm orless, and most preferably 500 ppm or less. In the case wherebis(p-methylbenzylidene)sorbitol or bis(dimethylbenzylidene)sorbitol isemployed, it is added preferably at 1200 ppm or less, more preferably600 ppm or less, particularly 300 ppm or less. In the case where sodiumorganophosphate which is one of the metal organophosphates, it is addedpreferably at 50 ppm or less, more preferably 200 ppm or less,particularly 125 ppm or less. An aluminium organophosphate is addedpreferably at 1900 ppm or less, more preferably 1500 ppm or less,particularly 500 ppm or less. When a talc is employed, talc MMR producedby ASADA SEIFUN, for example in this case, is added preferably at 4000ppm or less, more preferably 2000 ppm or less, particularly 1000 ppm orless. When an amide-based compound is employed, N-GESTER-NU-100 producedby SHINNPPON RIKA, for example in this case, is added preferably at 3000ppm or less, more preferably 1500 ppm or less, particularly 500 ppm orless.

To a propylenic polymer, a propylenic polymer composition, a moldedarticle or a film according to the invention, customary additives suchas antioxidant, neutralizing agent, slipperiness-imparting agent,anti-blocking agent, anti-frosting agent, decomposing agent, foamingagent, antistatic agent and the like may be incorporated as desired.

A film produced by a propylenic polymer composition of the invention isproduced first by kneading of a propylenic polymer and a nucleatingagent together with necessary various additives using a single- ortwin-screw extruder, Banbury mixer and the like into a pellet which isthen formed into a film by a cast molding. Alternatively, a propylenicpolymer, a nucleating agent and necessary additives are dry-blended inHenschel mixer or an equivalent, and then formed into a film by a castmolding.

When a high melting polymer is used as a nucleating agent, the highmelting polymer may be produced simultaneously or sequentially duringthe production of a propylenic polymer in a reactor, whereby obtaining apropylenic polymer composition.

[II] Second Invention

The second invention consisting of a propylenic polymer [1], a methodfor producing the same [2], a propylenic resin composition [3], a moldedarticle [4] and a propylenic resin modifier [5] is detailed below.

[1] Propylenic Polymer

An inventive propylenic polymer is a propylenic polymer satisfying thefollowing requirements (1) and (2):

(1) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(2) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/g) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140).

In addition, an inventive propylenic polymer is a propylenic polymersatisfying the following requirements (1) to (3):

(1) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/g) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140).

By satisfying the requirements described above, an inventive propylenicpolymer provides a molded article exhibiting well-balanced amount of thestickiness-imparting components, low modulus and transparency. Thus, itexhibits a low modulus and an excellent softness (referred to aspliability), contains a reduced amount of a stickiness-impartingcomponent and has an excellent surface characteristics (for examplethose experienced as a less bleeding and a less migration of astickiness-imparting component into other products), and is alsoassociated with an advantageously excellent transparency.

The requirements described above are discussed below.

A propylenic polymer has an amount of the components which are dissolvedout at 25° C. or lower (W25) in a temperature-raising chromatographywhich ranges from 20 to 100% by weight, preferably 30 to 100% by weight,more preferably 50 to 100% by weight. W25 is an index for the softnessof a propylenic polymer. An increase in this value is associated with anincrease in the component having a higher modulus and/or a broaderreoregularity distribution. In the invention, a value W25 less than 20%is not preferable since it results in the loss of the pliability. Avalue W25 is the amount (% by weight) of the components which aredissolved out, instead of adsorbed onto a packing, at the TREF columntemperature of 25° C., as observed on a elution curve determined by atemperature-raising chromatography performed by the operating procedurewith the instruments under the operating conditions specified below.

(a) Operating Procedure

A sample solution is introduced into a TREF column adjusted at 135° C.and then the temperature is lowered gradually at the lowering rate of 5°C./hour to 0° C., at which the temperature is held for 30 minutes toeffect a crystallization of a sample on the surface of the packing.Subsequently, the column temperature is raised at the raising rate of40° C./hour to 135° C. to obtain an elution curve.

(b) Instruments

TREF column: Manufactured by GL SCIENCE, Silica gel column (4.6φ×150 mm)

Flow cell: Manufactured by GL SCIENCE, path length 1 mm, KBr cellFeed pump: Manufactured by SENSHU KAGAKU, Pump Model SSC-3100Valve oven: Manufactured by GL SCIENCE, Oven model 554 (high temperaturetype)TREF oven: Manufactured by GL SCIENCEDual-system thermostat: Manufactured by RIKAGAKU KOGYO, Thermostat modelREX-C100Detector: Infrared detector for HPLC, Manufactured by FOXBORO CORP.,Model MIRAN 1A CVF10-way valve: Manufactured by VALCO, Electric valve

Loop: Manufactured by VALCO, 500 μL Loop (C) Operating Conditions

Solvent: o-DichlorobenzeneSample concentration: 7.5 g/LInjection volume: 500 μLPumping rate: 2.0 mL/minDetection wavenumber: 3.41 μmColumn packing: CHROMOSOLVE P (30 to 60 mesh)Column temperature deviation: Within ±0.2° C.

In a propylenic polymer according to the invention, the amount of thecomponents which are dissolved out into hexane at 25° C. (H25) rangesfrom 0 to 80% by weight. Preferably, it is 0 to 50% by weight,particularly 0 to 25% by weight. H25 is an index for the level of astickiness-imparting component which causes a reduced transparency, anda higher H25 indicates an increased amount of a stickiness-impartingcomponent. With a level of H25 exceeding 80% by weight, astickiness-imparting component exists in a large amount, which may causeproblematic blocking and transparency characteristics, because of whichthe use in a food or medical product is not acceptable.

A level of H25 is a % reduction in weight which is obtained bydetermining the weight of a propylenic polymer (W0) and the weight ofthe same after allowing to stand in 200 mL of hexane at 25° C. for 3days or longer followed by drying (W1) and then calculating inaccordance with the equation shown below.

H25=[(W0−W1)/W0]×100(%)

In a propylenic polymer according to the invention, no melting point(Tm(° C.)) is observed in DSC, or, when any Tm is observed then the Tmand the fusion endothermic calorie ΔH(J/G) are in the relationshiprepresented by the following formula:

ΔH≧6×(Tm−140),

more preferably,

ΔH≧3×(Tm−120),

particularly,

ΔH≧2×(Tm−100).

The vales of Tm and ΔH are determined in DSC. Thus, using a differentialscanning calorimeter (Perkin Elmer, DSC-7), 10 mg of a sample is fusedfor 3 minutes at 230° C. under a nitrogen atmosphere and then thetemperature is lowered to 0° C. at the rate of 10° C./minutes. Afterholding at 0° C. for 3 minutes, the temperature is raised at the rate of10° C./minutes to obtain a fusion endothermic curve, in which the peaktop of the maximum peak represents the melting point: Tm and the fusionendothermic calorie in this case is represented as ΔH(J/g).

A propylenic polymer according to the invention is not particularlylimited, provided that it can satisfy the requirements described above,and may for example be a propylene homopolymer or a propyleniccopolymer. Specifically, a propylenic polymer according to the inventiondescribed above can more preferably be embodied by a propylenehomopolymer [a] or a propylene copolymer [a′] described below.

[α] Propylene Homopolymer

A propylene homopolymer of the invention is a polymer satisfying thefollowing requirements (1) to (3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]<0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 0° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

When a propylene homopolymer according to the invention satisfies therequirements described above, a resultant molded article exhibitswell-balanced amount of the stickiness-imparting components, low modulusand transparency. Thus, it exhibits a low modulus and an excellentsoftness (referred to as pliability), contains a reduced amount of astickiness-imparting component and has an excellent surfacecharacteristics (for example those experienced as a less bleeding and aless migration of a stickiness-imparting component into other products),and is also associated with an advantageously excellent transparency.

A % meso-pentad (% mmmm) employed in the present invention is the sameto that discussed in the first invention.

A meso-pentad fraction (mmmm) of an inventive propylene homopolymer lessthan 20% by mole may cause a stickiness. One exceeding 60% by mole mayrepresent disadvantageously high modulus. A % racemi-pentad (% rrrr) isa % racemic moiety, represented in pentad as a unit, in a polypropylenemolecule chain. A value [rrrr/(1−mmmm)] can be obtained from a % inpentad described above, and serves as an index for the narrowness in theregularity distribution of a propylene homopolymer. An increase in thisvalue is associated with a broader regularity distribution, andrepresents a mixture of a highly regular PP and APP such as aconventional polypropylene produced using an existing catalyst system,and thus is associated with an increased stickiness and a reducedtransparency. A value [rrrr/(1−mmmm)] of a propylene homopolymer of theinvention which exceeds 0.1 causes a stickiness. A ¹³C-NMR spectrum isobtained similarly as in the first invention.

The meanings and the determination method of a W25 with regard to apropylene homopolymer are similar to those with regard to the propylenicpolymer [1] described above. A W25 of an inventive propylene homopolymerless than 20% results in the loss of pliability.

A propylenic homopolymer is further preferred when it satisfies, amongthe requirements described above, the following requirements:

(4) the meso-pentad fraction (mmmn (in percentage terms by mole)) rangesfrom 30 to 50% by mole;(5) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.08

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(6) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 30 to100% by weight;and is particularly preferred when it satisfies the followingrequirements:(7) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)≦0.06

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(8) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 50 to100% by weight.

A propylene homopolymer according to the invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with a Mw/Mn of 3.5 or less and/or a [1] of 1.0 to 5.0 dl/g beingmore preferred and a Mw/Mn of 3 or less and/or a [η] of 1.0 to 3.0 dl/gbeing particularly preferred. A molecular weight distribution (Mw/Mn)exceeding 4 may cause a stickiness, and an intrinsic viscosity [η] lessthan 0.5 dl/g may also cause a stickiness. A [η] exceeding 15.0 dl/gresults in a reduced flowability which may lead to a poor moldingperformance.

A Mw/Mn described above may be understood similarly as in the firstinvention.

In addition to the requirements described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/gr. or less allows an inventivepropylene homopolymer to be more pliable and thus be more preferred. Avalue of ΔH is an index for the softness, and a higher value representsa higher modulus and a reduced softness. A ΔH is obtained as describedabove.

While an inventive propylenic homopolymer may have or may not have amelting point (Tm) and a crystallization temperature (Tc), it ispreferred for the purpose of the softness that such values do not existor do exist only as low values, with a Tm not higher than 100° C. beingpreferred. The values of Tm and Tc are determined by DSC. Thus, using adifferential scanning calorimeter (Perkin Elmer, DSC-7), 10 mg of asample is fused for 3 minutes at 230° C. under a nitrogen atmosphere andthen the temperature is lowered to 0° C. at the rate of 10° C./minutes.The peak top of the maximum curve in the crystallization exothermiccurve obtained during this course is the crystallization temperature:Tc.After holding at 0° C. for 3 minutes, the temperature is raised at therate of 10° C./minutes to obtain a fusion endothermic curve, in whichthe peak top of the maximum peak represents the melting point: Tm.

While during an ordinary propylene polymerization process a 1,2insertion polymerization, which means that a carbon atom of a propylenemonomer on the side of a methylene undergoes a binding with an activecenter of a catalyst followed by a successive coordination of thepropylene monomers in the same manner whereby effecting thepolymerization, takes place generally, a 2,1 insertion or a 1,3insertion may also take place at a less incidence (sometimes referred toas abnormal insertion). In a homopolymer according to the invention, itis preferable that the incidence of such 2, 1 or 1,3 insertion is low.It is also preferable that these insertion rates satisfy therelationship represented by the following formula (1):

[(m−2,1)+(r−2,1)+(1,3)]≦5.0  (1)

wherein (m−2,1) is a % meso-2,1 insertion content determined by ¹³C-NMR,(r−2,1) is a % racemi-2,1 insertion content determined by ¹³C-NMR, and(1,3) is a % 1,3 insertion content determined by ¹³C-NMR, and, morepreferably, they satisfy the relationship represented by the followingformula (2):

[(m−2,1)+(r−2,1)+(1,3)]≦1.0  (2)

It is particularly preferred that they satisfy the relationshiprepresented by the following formula (3):

[(m−2,1)+(r−2,1)+(1,3)]≦0.1  (3).

When the relationship represented by Formula (1) is not satisfied, thecrystallinity is reduced far more than expected, and a stickiness mayarise.

(m−2, 1), (r−2, 1) and (1,3) are understood similarly as in the firstinvention.

A propylene homopolymer of the invention preferably exhibitssubstantially no peaks in a ¹³C-NMR spectrum which are assigned to amolecular chain terminal (n-butyl group) as a result of a 2,1 insertion.With regard to this molecular chain terminal as a result of a 2,1insertion, each % insertion content is calculated from the integratedintensity of each peak after assignment of the peak in the ¹³C-NMRspectrum in accordance with the report by Jungling et al (J. Polym.Sci.: Part A: Polym. Chem., 33, p 1305 (1995)).

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylene homopolymer in the invention to be furtherpreferred. A % boiling diethylether extract can be determined using aSoxlet extractor under the conditions specified below.

Extraction sample: 1 to 2 gState of sample: Powder (a pellet should be pulverized into a powderbefore use)Extraction solvent: DiethyletherExtraction duration: 10 hoursExtraction times: 180 times or moreCalculation of extract: As shown below

[Amount extracted into diethylether (g)/Charged powder weight (g)]×100

Further preferably, an inventive propylene homopolymer has a tensileelastic modulus of 100 MPa or less, more preferably 70 MPa or less.

[a′] Propylenic Copolymer

A propylenic copolymer according to the invention is a copolymer ofpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomswhich satisfies the following requirements:

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

When a propylenic copolymer according to the invention satisfies therequirements described, above, a resultant molded article exhibitswell-balanced amount of the stickiness-imparting components, low modulusand transparency. Thus, it exhibits a low modulus and an excellentsoftness (referred to as pliability), contains a reduced amount of astickiness-imparting component and has an excellent surfacecharacteristics (for example those experienced as a less bleeding and aless migration of a stickiness-imparting component into other products),and is also associated with an advantageously excellent transparency. Astereoregularity index (P) in the invention is a value obtained bydetermining a ¹³C-NMR spectrum similarly as in the first invention usingNippon Densi Model JNM-EX400 ¹³C-NMR device described above and thencalculating a % meso-triad (mmmm) of a propylene chain. An increase inthis value is associated with a higher stereoregularity. A propyleniccopolymer according to the invention preferably has a stereoregularityindex (P) of 65 to 80% by mole. A stereoregularity index (P) less than55% by weight results in a too reduced modulus, which may lead to a poormolding performance. At 90% by mole or higher, a rigidness may arise anda softness is lost. It is further preferred that the W25 is 30 to 100%by weight, with 50 to 100% by weight being particularly preferred. A W25less than 20% by weight results in a loss of pliability. The meaningsand the determination method of a W25 are as described above.

A propylenic copolymer according to the invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with a Mw/Mn of 3.5 or less and/or a [η] of 1.0 to 5.0 dl/g beingmore preferred and a Mw/Mn of 3 or less and/or a [η] of 1.0 to 3.0 dl/gbeing particularly preferred. A molecular weight distribution (Mw/Mn)exceeding 4 may cause a stickiness. An intrinsic viscosity [η] less than0.5 dl/g may also cause a stickiness, and one exceeding 15.0 dl/gresults in a reduced flowability which may lead to a poor moldingperformance. The determination method of this Mw/Mn is as describedabove.

In addition to the requirements described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/gr. or less allows an inventivepropylenic copolymer to be more pliable and thus be more preferred.While an inventive propylenic copolymer may have or may not have amelting point (Tm) and a crystallization temperature (Tc), it ispreferred for the purpose of the softness that such values do not existor do exist only as low values, with a Tm not higher than 100° C. beingpreferred. ΔH, Tm and Tc are obtained as described above. In addition tothe requirements described above,

a % boiling diethylether extract, which is an index for the modulus, of5% by weight or higher allows a propylenic copolymer in the invention tobe further preferred. The boiling diethylether extract is determined asdescribed above.

In addition, the tensile elastic modulus is preferably 100 MPa or less,more preferably 70 MPa or less.

In conjunction with a propylenic copolymer according to the invention,an α-olefin having 4 to 20 carbon atoms may for example be ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene andthe like, and, in the invention, these may be employed alone or incombination with each other.

A propylenic copolymer according to the invention is preferably a randomcopolymer. The structural unit derived from propylene exists preferablyat a level of 90% by mole or higher, more preferably 95% by mole orhigher.

[Method for Producing Propylene Homopolymer (a) and Propylenic Copolymer(a′)]

A method for producing a propylene homopolymer (a) and a propyleniccopolymer (a′) according to the invention may be a method in which acatalyst system called a metallocene catalyst is used to homopolymerizepropylene or to copolymerize propylene and ethylene and/or an α-olefinhaving 4 to 20 carbon atoms. A metallocene-based catalyst may forexample be those described in JP-A-58-19309, JP-A-61-130314,JP-A-3-163088, JP-A-4-300887, JP-A-4-211694, JP-W-1-502036 and the like,such as a catalyst derived from a transition metal compound having, asits one or two ligands, cyclopentadienyl group, substitutedcyclopentadienyl group, indenyl group, substituted indenyl group and thelike or and a transition metal compound in which said ligands arecontrolled geometrically in combination with a promoter.

In the invention, among metallocene catalysts, one derived from atransition metal compound whose ligand forms a crosslinking structurevia a crosslinking group is preferred, and a particularly preferredmethod involves a use of a metallocene catalyst obtained by combining atransition metal compound whose crosslinking structure is formed via 2crosslinking groups with a promoter whereby effecting ahomopolymerization of propylene or a copolymerization of propylene andethylene and/or an α-olefin having 4 to 20 carbon atoms.

Typically, a catalyst consists of the following components.

(A) a transition metal compound(B) a component (B-1) which is a compound capable of forming an ioniccomplex by reacting with a transition metal compound as a component (A)and a component (B-2) which is an aluminoxane.

In addition to a component (A) and a component (B), an organic aluminiumcompound can be used as a component (C).

Components (A), (B) and (C) are similar to those described in the firstinvention, and each of components (B) and (C) may be used alone or incombination of two or more. The amount of each component to be used isalso similar to that employed in the first invention.

In a production method according to the invention, components (A), (B)and (C) may be subjected to a preliminary contact. Such preliminarycontact may for example be effected by bringing a component (B) intocontact with a component (A) in a manner similar to that described inthe first invention.

In the present invention, at least one of the catalyst components may beemployed as being supported on a suitable carrier. A carrier employed inthis invention is similar to that in the first invention. A method forallowing at least one of the catalyst components to be supported on acarrier is also similar to that in the first invention.

In the present invention, a catalyst may be prepared by irradiating adynamic wave upon contact between components (A), (B) and (C). Suchelastic wave is usually a sound wave, preferably an ultrasonic wave.Typically, an ultrasonic wave at a frequency of 1 to 1000 kHz,preferably 10 to 500 kHz may be exemplified.

A catalyst thus obtained may be used in a polymerization after beingisolated as a solid by distilling a solvent off, or alternatively it maybe subjected directly to a polymerization.

In the invention, as is discussed already in the first invention, acatalyst may be produced also by allowing at least one of a component(A) and a component (B) to be supported on a carrier within the systemof polymerization.

In this invention, the ratio of a component (B-1) to a carrier, theratio of a component (B-2) to a carrier and the ratio of a component (A)to a carrier are similar to those in the first invention.

The polymerization catalyst of the invention thus prepared usually has amean particle size of 2 to 200 m, preferably 10 to 150 μm, particularly20 to 100 μm, and a specific surface area usually of 20 to 1000 m²/g,preferably 50 to 500 m²/g. In an inventive catalyst, the amount of atransition metal in 100 g of a carrier is usually 0.05 to 10 g,preferably 0.1 to 2 g. An amount of a transition metal departing fromthe range described above may result in a reduced activity.

By means of employing a carrier as a support as described above, apolymer having industrially advantageous high bulk density and excellentparticle size distribution can be obtained.

A propylenic polymer according to the invention is produced by using apolymerization catalyst described above to homopolymerize propylene, orto copolymerize propylene and ethylene and/or an α-olefin having 4 to 20carbon atoms.

While a polymerization method is not particularly limited and may be aslurry polymerization, a vapor phase polymerization, a bulkpolymerization, a solution polymerization, a suspension polymerizationand the like, those particularly preferred are a slurry polymerizationand a vapor phase polymerization.

A polymerization condition involves a polymerization temperature usuallyof −100 to 250° C., preferably −50 to 200° C., more preferably 0 to 130°C. The ratio of a catalyst to a reactant, represented as startingmonomer/component (A) (molar ratio), is preferably 1 to 10⁸,particularly 100 to 10^(s). A polymerization time usually of 5 minutesto 10 hours, and a reaction pressure preferably of atmospheric pressureto 200 kg/cm²G, particularly atmospheric pressure to 100 kg/cm²G areemployed.

The molecular weight of a polymer may be adjusted by a manner similar tothat in the first: invention.

When a polymerization solvent is employed, the types of the solvents maybe similar to those in the first invention.

Upon polymerization, a polymerization catalyst described above may beused to perform a preliminary polymerization. Such preliminarypolymerization may be similar to that in the first invention.

[3] Propylenic Resin Composition

A propylenic resin composition according to the invention is a resincomposition obtained by adding a nucleating agent to a propylenicpolymer [1], a propylene homopolymer [a] or a propylenic copolymer [a′]described above. In general, the crystallization of a propylenic polymerinvolves 2 processes, namely, a nucleation process and a crystal growthprocess, and it is understood that in the nucleation process thenucleation rate varies dependend on the state factors such as thedifference from the crystallization temperature or the orientation of amolecular chain. Especially when a substance having a molecular chainorientation promoting effect via a adsorption of the molecular chain ispresent, the nucleation rate is increased markedly. As a nucleatingagent in the invention, one having a nucleation rate accelerating effectis employed. The substance having a nucleation rate accelerating effectmay for example be one having a molecular chain orientation promotingeffect via a adsorption of the molecular chain of a polymer.

A nucleating agent in this invention is similar to that in the firstinvention, and only one or a combination of two or more of nucleatingagents may be employed.

A propylenic resin composition in this invention which employs a metalorganophosphate and/or an inorganic microparticle such as talc ispreferred because of a reduced generation of an odor. Such propylenicresin composition is applied preferably to a food product.

A propylenic resin composition in this invention which employs as anucleating agent an inorganic microparticle such as talc as describedabove, it exhibits an excellent slipperiness when molded into a film andprovides an improvement in the film characteristics such asprintability. When a dibenzylidene sorbitol or its derivative describedabove is employed as a nucleating agent, an advantageously excellenttransparency is achieved. Also when an amide compound described above isemployed as a nucleating agent, an advantageously excellent rigidity isachieved.

An inventive propylenic resin composition may be one obtained bydry-blending a propylenic polymer [1], a propylene homopolymer [a] or apropylenic copolymer [a′] with a nucleating agent, together with variousadditives if desired, using a mixer such as Henschel mixer.Alternatively, a kneading may be effected using a single- or twin-screwextruder, Banbury mixer and the like. When a high melting polymer isused as a nucleating agent, the high melting polymer may be added to areactor simultaneously or sequentially during the production of apropylenic polymer. Additives employed if necessary are antioxidant,neutralizing agent, slipperiness-imparting agent, anti-blocking agent,anti-frosting agent and antistatic agent and the like.

The amount of a nucleating agent added in the invention is 10 ppm orhigher, preferably 10 to 10000 ppm, more preferably to 5000 ppm,particularly 10 to 2500 ppm, based on a propylenic polymer [1], apropylene homopolymer [a] or a propylenic copolymer [a′]. An amount lessthan 10 ppm provides no improvement in the moldability, while an amountexceeding 10000 ppm fails to exhibit corresponding increase in theeffect.

[4] Molded Article

A molded article in this invention is a molded article obtained bymolding a propylenic polymer [1], a propylene homopolymer [a], apropylenic copolymer [a′] or a propylenic resin composition [3]described above. An inventive molded article has a softness (alsoreferred to as pliability) and a high % elasticity recovery (ability ofrecovery after being stretched), and is characterized by a lessstickiness in spite of its high softness, i.e., a low modulus, as wellas an excellent transparency.

A molded article in this invention may for example be films, sheets,containers, automobile interior parts, electricity power line housingsand the like. Films may for example be films for food product packagingsand films for agricultural uses (such as for green houses). Containersmay for example be clear cases, clear boxes, decorated boxes utilizingtheir excellent transparency.

A molded article may be produced by injection molding, compressionmolding, injection stamping, gas-assisted injection molding, extrusionmolding, blow molding and the like.

The molding conditions may not particularly be limited, provided that atemperature capable of allowing a resin to be molten and to flow isemployed, and a usual case involves a resin temperature of 50° C. to300° C. and a mold temperature of 60° C. or lower.

When a film is formed as a molded article in this invention, a methodwhich may be employed includes ordinary compression molding, extrusionmolding, blow molding, cast molding and the like. The film obtained maybe oriented or may not be oriented. When oriented, it is preferred to bebiaxially oriented. The biaxially orienting conditions involev theparameters described below.

[1] Sheet Molding Conditions

Resin temperature of 50 to 200° C., chill roll temperature of 50° C. orlower

[2] Lengthwise Orienting Conditions

Orienting magnitude of 3 to 7 times, orienting temperature of 50 to 100°C.

[3] Widthwise Orienting Conditions

Orienting magnitude of 6 to 12 times, orienting temperature of 50 to100° C.

A film may be surface-treated if necessary to enhance its surface energyor to impart the surface with a polarity.

For example, corona discharge treatment, chromic acid treatment, flametreatment, hot gas treatment, ozone- or UV irradiation treatment may forexample be employed. The surface may be embossed by, for example,sand-blast method or solvent treatment.

To a film, a customary additives such as antioxidant, neutralizingagent, slipperiness-imparting agent, anti-blocking agent, anti-frostingagent, antistatic agent and the like may be incorporated as desired.

A film further containing an inorganic microparticle such as talcexhibits an excellent slipperiness, which leads to an improvement insecondary processing performances such as bag making or printingperformance, due to which it is suitable as a general-purpose packagingfilm subjected to a high speed machine including various automaticfilling-packaging laminators.

A film produced by molding a propylenic resin composition containing adibenzylidene sorbitol or its derivative as a nucleating agent has aparticularly excellent transparency which is highly display-oriented,and which makes it suitable as a package film of a toy or a stationery.

A film produced by molding a propylenic resin composition containing anamide compound as a nucleating agent has a particularly excellentrigidity and exhibits a less problematic wrinkling when being woundduring a high speed bag making, due to which it is suitable as ageneral-purpose packaging film subjected to a high speed bag makingmachine.

[5] Propylenic Resin Modifier

A propylenic resin modifier is a resin modifier comprising a propylenicpolymer [1], a propylene homopolymer [a] or a propylenic copolymer [a′]described above. An inventive propylenic resin modifier is characterizedby an ability of providing a molded article having a softness, a lessstickiness and an excellent compatibility with a polyolefin resin. Thus,an inventive propylenic resin modifier exhibits a less stickiness whencompared with a conventional modifier which is a soft polyolefin resin,since it comprises specified propylene homopolymer and specifiedpropylenic polymer and is associated partially with a crystallinityespecially in a polypropylene chain moiety. In addition, an inventivepropylenic resin modifier is excellent in terms of the compatibilitywith an olefin resin, especially with a polypropylenic resin. As aresult, it exhibits a less deterioration of the surface condition (suchas stickiness) and a higher transparency, when compared with aconventional modifier which is an ethylenic rubber. The characteristicsdiscussed above makes an inventive propylenic resin modifier to be usedpreferably as an agent for modifying physical properties such aspliability and transparency.

[III] Third Invention

The third invention consisting of a propylenic polymer [1], a method forproducing the same [3], and a molded article [3] is detailed below.

[1] Propylenic Polymer

An inventive propylenic polymer is a propylenic polymer satisfying thefollowing requirements (1) to (3):

(1) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight;(2) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/g) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140); and,

(3) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) ranges from 2.5 to 14.0 and theintrinsic viscosity [η] determined in a decalin solvent at 135° C.ranges from 0.5 to 15.0 dl/g.

By satisfying the requirements described above, an inventive propylenicpolymer exhibits an excellent melt flowability and provides a moldedarticle having a less stickiness as well as excellent softness andtransparency.

The requirements described above are detailed below.

In a propylenic polymer according to the invention, the amount of thecomponents which are dissolved out into hexane at 25° C. (H25) rangesfrom 0 to 80% by weight. Preferably, it is 0 to 50% by weight,particularly 0 to 25% by weight. H25 is an index for the level of astickiness-imparting component which causes a reduced transparency, anda higher H25 indicates an increased amount of a stickiness-impartingcomponent. With a level of H25 exceeding 85% by weight, astickiness-imparting component exists in a large amount, which may causedeterioration in blocking and transparency characteristics.

H25 can be understood similarly as in the second invention. Furthermorein a propylenic polymer according to the invention, no melting point(Tm(° C.)) is observed in DSC, or, when any Tm is observed then the Tmand the fusion endothermic calorie ΔH(J/G) are in the relationshiprepresented by the following formula:

ΔH≧6×(Tm−140),

more preferably,

ΔH≧3×(Tm−120),

particularly,

ΔH≧2×(Tm−100).

Tm and ΔH can also be understood similarly as in the second invention.

A propylenic copolymer according to the invention has a molecular weightdistribution (Mw/Mn) determined by a gel permeation chromatography (GPC)of 2.5 to 14.0 and an intrinsic viscosity [η] determined in a decalinsolvent at 135° C. of 0.5 to 15.0 dl/g. An Mw/Mn of 3.0 to 12.0 and a[η] of 1.0 to 5.0 dl/g are more preferred, and an Mw/Mn of 4.0 to 10.0and a [η] of 1.0 to 3.0 dl/g is particularly preferred. A molecularweight distribution (Mw/Mn) less than 2.5 results in a poor moldability,while that exceeding 14.0 may cause a stickiness. An intrinsic viscosity[η] less than 0.5 dl/g may also cause a stickiness, and one exceeding15.0 dl/g results in a reduced flowability which may lead to a poormolding performance. GPC is determined similarly as in the firstinvention.

In addition to the requirements described above, a complex viscositycoefficient (η*) (Pa·s) and an intrinsic viscosity [η]) (dl/g) at thefrequency ω of 100 rad/sec in determination of the frequencydistribution of the melt viscoelasticity, which are in the relationshiprepresented by the formula:

η*<159η+743;

more preferably,

η*<159η+600;

particularly,

η*<159η+500;

allows an inventive propylenic copolymer to have an improved meltflowability and thus be more preferred.

A value of (η*) (Pa·s) is obtained by determining a frequencydistribution of a melt viscoelasticity using a rotary rheometer (ARES)manufactured by RHEOMETRIX together with a parallel plate (25 mm indiameter, 1 mm in gap) at the temperature of 230° C. and at the initialstrain of 20% or less. (η*) is an index for the flowability of a moltenresin upon molding fabrication, and a lower value indicates a higherflowability and a higher molding fabrication performance.

A propylenic polymer according to the invention is not particularlylimited, provided that it can satisfy the requirements described above,and may for example be a propylene homopolymer or a propyleniccopolymer. Specifically, a propylenic polymer according to the inventiondescribed above can more preferably be embodied by a propylenehomopolymer [a] or a propylene copolymer [a′] described below.

[a] Propylene Homopolymer

A propylene homopolymer of the invention is a polymer satisfying thefollowing requirements (1) to (3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 85% by nole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the molecular weight distribution (Mw/Mn) determined by a gelpermeation chromatography (GPC) ranges from 2.5 to 14.0 and theintrinsic viscosity [η] determined in a decalin solvent at 135° C.ranges from 0.5 to 15.0 dl/g.

When a propylene homopolymer according to the invention satisfies therequirements described above, a resultant molded article exhibits anexcellent melt flowability, a less stickiness, and excellent softnessand transparency.

A % meso-pentad (% mmmm) and a % racemi-pentad (% rrrr) referred hereinwere similar to those described in the first invention. An inventivepropylene homopolymer has a % meso-pentad (% mmmm) which is preferably30 to 70%, particularly 35 to 60%. A meso-pentad fraction (mmmm) of aninventive propylene homopolymer less than 20% by mole may cause astickiness. One exceeding 85% by mole results in a disadvantageouslyhigher modulus. An inventive propylene homopolymer is preferred when[rrrr/(1−mmmm)]≦0.08, and is particularly preferred when[rrrr/(1−mmmm)]≦0.06. A value of [rrrr/(1−mmmm)] exceeding 0.1 may causea stickiness.

A propylene homopolymer according to the invention has a molecularweight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) of 2.5 to 14.0 and an intrinsic viscosity [η]determined in a decalin solvent at 135° C. of 0.5 to 15.0 dl/g. An Mw/Mnof 3.0 to 12.0 and a [1] of 1.0 to 5.0 dl/g are more preferred, and anMw/Mn of 4.0 to 10.0 and a [η] of 1.0 to 3.0 dl/g is particularlypreferred. A molecular weight distribution (Mw/Mn) less than 2.5 resultsin a poor moldability, while that exceeding 14.0 may cause a stickiness.An intrinsic viscosity [η] less than 0.5 dl/g may also cause astickiness, and one exceeding 15.0 dl/g results in a reduced flowabilitywhich may lead to a poor molding performance.

In addition to the requirements described above, a complex viscositycoefficient (η*) (Pa·s) and an intrinsic viscosity [η] (dl/g) at thefrequency ω of 100 rad/sec in determination of the frequencydistribution of the melt viscoelasticity, which are in the relationshiprepresented by the formula:

η*<159η+743;

more preferably,

η*<159η+600;

particularly,

η*<159η+500;

allows an inventive propylene homopolymer to have an improved meltflowability and thus be more preferred.

The meaning of (η*) (Pa·s) is understood as discussed above.

In addition, it is preferred that in a propylene homopolymer accordingto the invention the amount of the components which are dissolved out at25° C. or lower (W25) in a temperature-raising chromatography rangesfrom 20 to 100% by weight. More preferably, such amount ranges from 30to 100% by weight, and most preferably 50 to 100% by weight. W25 is anindex for the softness of a propylenic polymer. An increase in thisvalue is associated with an increase in the component having a highermodulus and/or a broader stereoregularity distribution. In theinvention, a value W25 less than 20% may result in the loss of thepliability. A value W25 is the amount (% by weight) of the componentswhich are dissolved out, instead of adsorbed onto a packing, at the TREFcolumn temperature of 25° C., as observed on a elution curve determinedby a temperature-raising chromatography performed by the operatingprocedure with the instruments under the operating conditions describedin the examples. In the invention, a value W25 less than 20% may resultin the loss of the pliability.

Furthermore, a fusion endothermic calorie ΔH determined by DSC of 20J/gr. or less allows an inventive propylene homopolymer to be excellentin terms of the pliability and thus be more preferred. A value of ΔH isan index for the softness, and a higher value represents a highermodulus and a reduced softness. A ΔH is obtained as described above.

In addition, while an inventive propylenic homopolymer may have or maynot have a melting point (Tm) and a crystallization temperature (Tc), itis preferred for the purpose of the softness that such values do notexist or do exist only as low values, with a Tm not higher than 100° C.being preferred. The values of Tm and Tc are determined by DSC, and maybe understood as described in the second invention.

While during an ordinary propylene polymerization process a 1,2insertion polymerization, which means that a carbon atom of a propylenemonomer on the side of a methylene undergoes a binding with an activecenter of a catalyst followed by a successive coordination of thepropylene monomers in the same manner whereby effecting thepolymerization, takes place generally, a 2,1 insertion or a 1,3insertion may also take place at a less incidence (sometimes referred toas abnormal insertion). In a homopolymer according to the invention, itis preferable that the incidence of such 2,1 or 1,3 insertion is low. Itis also preferable that these insertion rates satisfy the relationshiprepresented by the following formula (1):

[(m−2,1)+(r−2,1)+(1,3)]<5.0  (1)

wherein (m−2,1) is a % meso-2,1 insertion content determined by ¹³C-NMR,(r−2,1) is a % racemi-2,1 insertion content determined by ¹³C-NMR, and(1,3) is a % 1,3 insertion content determined by ¹³C-NMR, and, morepreferably, they satisfy the relationship represented by the followingformula (2):

[(m−2,1)+(r−2, 1)+(13)]≦1.0  (2).

It is particularly preferred that they satisfy the relationshiprepresented by the following formula (3):

[(m−2,1)+(r−2,1)+(1,3)]≦0.1  (3).

When the relationship represented by Formula (1) is not satisfied, thecrystallinity is reduced far more than expected, and a stickiness mayarise. (m−2, 1), (r−2, 1) and (1,3) are understood similarly as in thefirst invention.

A propylene homopolymer of the invention preferably exhibitssubstantially no peaks in a ¹³C-NMR spectrum which are assigned to amolecular chain terminal (n-butyl group) as a result of a 2,1 insertion.With regard to this molecular chain terminal as a result of a 2,1insertion, each % insertion content is calculated from the integratedintensity of each peak after assignment of the peak in the ¹³C-NMRspectrum in accordance with the report by Jungling et al (J. Polym.Sci.: Part A: Polym. Chem., 33, p 1305 (1995)).

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylene homopolymer in the invention to be furtherpreferred. A % boiling diethylether extract can be determined asdescribed in the second invention.

Further preferably, an inventive propylene homopolymer has a tensileelastic modulus of 100 MPa or less, more preferably 70 MPa or less.

[a′] Propylenic Copolymer

A propylenic copolymer according to the invention is a copolymer ofpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomswhich satisfies the following requirements:

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and (2) the molecular weight distribution (Mw/Mn)determined by a gel permeation chromatography (GPC) ranges from 2.5 to14.0 and the intrinsic viscosity [η] determined in a decalin solvent at135° C. ranges from 0.5 to 15.0 dl/g.

By satisfying the requirements described above, an inventive propylenicpolymer exhibits an excellent melt flowability and provides a moldedarticle having a less stickiness as well as excellent softness andtransparency.

A stereoregularity index (P) in the invention is a value obtained bydetermining a ¹³C-NMR spectrum and then calculating a % meso-triad (mm)of a propylene chain, and an increase in this value is associated with ahigher stereoregularity. A propylenic copolymer according to theinvention preferably has a stereoregularity index (P) of 65 to 80% bymole. A stereoregularity index (P) less than 55% by weight results in atoo reduced modulus, which may lead to a poor molding performance. At90% by mole or higher, a softness is lost.

¹³C-NMR spectrum is determined in a manner similar to that described inthe first invention.

Furthermore, a propylenic copolymer in this invention has a molecularweight distribution (Mw/Mn), determined by a gel permeationchromatography (GPC) described in the examples, of 2.5 to 14.0 and anintrinsic viscosity [η] determined in a decalin solvent at 135° C. of0.5 to 15.0 dl/g. An Mw/Mn of 3.0 to 12.0 and a [η] of 1.0 to 5.0 dl/gare more preferred, and an Mw/Mn of 4.0 to 10.0 and a [η] of 1.0 to 3.0dl/g is particularly preferred. A molecular weight distribution (Mw/Mn)less than 2.5 results in a poor moldability, while that exceeding 14.0may cause a stickiness. An intrinsic viscosity [η] less than 0.5 dl/gmay also cause a stickiness, while that exceeding 15.0 dl/g results in areduced flowability which may lead to a poor molding performance. GPC isdetermined by a method described in the first invention.

In addition to the requirements described above, a complex viscositycoefficient (η*) (Pa·s) and an intrinsic viscosity [η] (dl/g) at thefrequency ω of 100 rad/sec in determination of the frequencydistribution of the melt viscoelasticity, which are in the relationshiprepresented by the formula:

η*<159η+743;

more preferably,

η*<159η+600;

particularly,

η*<159η+500;

allows an inventive propylenic copolymer to have an improved meltflowability and thus be more preferred.

The meaning of (η*) (Pa·s) is understood as discussed above.

In addition, it is preferred that in a propylenic copolymer according tothe invention the amount of the components which are dissolved out at25° C. or lower (W25) in a temperature-raising chromatography rangesfrom 20 to 100% by weight. More preferably, such amount ranges from 30to 100% by weight, and most preferably 50 to 100% by weight. A value W25less than 20% may result in the loss of the pliability. The meaning andthe determination method of W 25 are as described above.

Furthermore, a fusion endothermic calorie ΔH determined by DSC of 20J/gr. or less allows an inventive propylenic copolymer to be excellentin terms of the pliability and thus be more preferred. In addition,while an inventive propylenic copolymer may have or may not have amelting point (Tm) and a crystallization temperature (Tc), it ispreferred for the purpose of the softness that such values do not existor do exist only as low values, with a Tm not higher than 100° C. beingpreferred. The determination methods of ΔH, Tm and Tc are as describedabove.

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylenic copolymer in the invention to be furtherpreferred.

In addition, the tensile elastic modulus is preferably 100 MPa or less,more preferably 70 MPa or less.

In conjunction with a propylenic copolymer according to the invention,an α-olefin having 4 to 20 carbon atoms may for example be ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene andthe like, and, in the invention, these may be employed alone or incombination with each other.

A propylenic copolymer according to the invention is preferably a randomcopolymer. The structural unit derived from propylene exists preferablyat a level of 90% by mole or higher, more preferably 95% by mole orhigher.

[Method for Producing Propylene Homopolymer [a] and Propylenic Copolymer[a′]]

A method for producing a propylene homopolymer [a] and a propyleniccopolymer [a′] according to the invention may be a method in which apropylene is homopolymerized or copolymerized by a multi-steppolymerization process comprising at least a step in which propylene ishomopolymerized, or propylene and ethylene and/or an α-olefin having 4to 20 carbon atoms are copolymerized in the presence of a catalystsystem called a metallocene catalyst. A metallocene catalyst may forexample be those described in the second invention. In the invention,among metallocene catalysts, one derived from a transition metalcompound whose ligand forms a crosslinking structure via a crosslinkinggroup is preferred, and a particularly preferred method involves amulti-step polymerization process comprising at least a step in whichpropylene is homopolymerized, or propylene and ethylene and/or anα-olefin having 4 to 20 carbon atoms are copolymerized in the presenceof a metallocene catalyst obtained by combining a transition metalcompound whose crosslinking structure is formed via 2 crosslinkinggroups with a promoter.

Typically, a catalyst consists of the following components.

(A) a transition metal compound(B) a component (B-1) which is a compound capable of forming an ioniccomplex by reacting with a transition metal compound as a component (A)and a component (B-2) which is an aluminoxane.

In addition to a component (A) and a component (B), an organic aluminiumcompound can be used as a component (C).

Components (A), (B) and (C) are similar to those described in the firstinvention, and each of components (B) and (C) may be used alone or incombination of two or more. The amount of each component to be used isalso similar to that employed in the first invention.

In a production method according to the invention, components (A), (B)and (C) may be subjected to a preliminary contact. Such preliminarycontact may for example be effected by bringing a component (B) intocontact with a component (A). Such preliminary contact may be performedin a manner similar to that described in the first invention.

In the present invention, at least one of the catalyst components may beemployed as being supported on a suitable carrier. A carrier employed issimilar to that in the first invention. A method for allowing at leastone of the catalyst components to be supported on a carrier is alsosimilar to that in the first invention.

In the present invention, a catalyst may be prepared by irradiating adynamic wave upon contact between components (A), (B) and (C). Suchelastic wave is usually a sound wave, preferably an ultrasonic wave.Typically, an ultrasonic wave at a frequency of 1 to 1000 kHz,preferably 10 to 500 kHz may be exemplified.

A catalyst thus obtained may be used in a polymerization after beingisolated as a solid by distilling a solvent off, or alternatively it maybe subjected directly to a polymerization.

In the invention, as is discussed already in the first invention, acatalyst may be produced also by allowing at least one of a component(A) and a component (B) to be supported on a carrier within the systemof polymerization.

The ratio of each component to a carrier is also the same to thatemployed in the first invention. The polymerization catalyst of theinvention thus prepared usually has a mean particle size of 2 to 200 μm,preferably 10 to 150 μm, particularly 20 to 100 μm, and a specificsurface area usually of 20 to 1000 m²/g, preferably 50 to 500 m²/g. Inan inventive catalyst, the amount of a transition metal in 100 g of acarrier is usually 0.05 to 10 g, preferably 0.1 to 2 g. An amount of atransition metal departing from the range described above may result ina reduced activity.

A propylene homopolymer [a] and a propylenic copolymer [a′] according tothe invention are produced by a method in which a propylene ishomopolymerized or copolymerized by a multi-step polymerization processcomprising at least a step in which propylene is homopolymerized, orpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomsare copolymerized in the presence of a metallocene catalyst. Aninventive production method may be a method in which a propylene ishomopolymerized or copolymerized by a multi-step polymerization processcomprising at least a step in which propylene is homopolymerized, orpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomsare copolymerized in the presence of a co-catalyst comprising ametallocene catalyst containing a component (A) described above and acomponent (B) and at least one other catalyst. The copolymerization maybe performed as a multi-step polymerization or may not. Preferably, amulti-step polymerization is employed for the polymerization.

In a production method in this invention a polymerization method is notparticularly limited and may be a slurry polymerization, a vapor phasepolymerization, a bulk polymerization, a solution polymerization, asuspension polymerization and the like, and those particularly preferredare a slurry polymerization and a vapor phase polymerization.

A polymerization condition of a multi-step polymerization or asingle-stage polymerization involves a polymerization temperatureusually of −100 to 250° C., preferably −50 to 200° C., more preferably 0to 130° C. The ratio of a catalyst to a reactant, represented asstarting monomer/component (A) (molar ratio), is preferably 1 to 10⁸,particularly 100 to 10⁵. A polymerization time usually of 5 minutes to10 hours, and a reaction pressure preferably of atmospheric pressure to200 kg/cm²G, particularly atmospheric pressure to 100 kg/cm²G areemployed.

The molecular weight of a polymer may be adjusted by appropriatelyselecting the type and the amount of each catalyst component and thepolymerization temperature, or by performing the polymerization in thepresence of a chain transfer agent. In this context, the description inthe second invention can analogously be applied. In the case of amulti-step polymerization, it is preferred to use the polymerizationconditions, such as temperature, pressure, polymerization time, amountof a chain transfer agent, monomer composition ratio and the like, inthe second stage which are different from those in the first stage.

When a polymerization solvent is employed, the types of the solvents maybe similar to those in the first invention. A monomer such as anα-olefin may also be employed as a solvent. Some polymerization methodsneed no use of solvents.

Upon polymerization, a polymerization catalyst described above may beused to perform a preliminary polymerization. Such preliminarypolymerization may be similar to that in the first invention.

A propylenic polymer, a propylene homopolymer [a] and a propyleniccopolymer [a′] in this invention may be supplemented with a nucleatingagent. Such nucleating agent is understood similarly as in the firstinvention.

As a nucleating agent in this invention, a metal organophosphate and/oran inorganic microparticle such as talc, as described in the firstinvention, is preferred because of a reduced generation of an odor andcan be applied preferably to a food product.

In this invention, the use of an inorganic microparticle such as talc asdescribed above as a nucleating agent results in an excellentslipperiness of a molded film and provides an improvement in thecharacteristics such as printability. When a dibenzylidene sorbitol orits derivative described above is employed as a nucleating agent, anadvantageously excellent transparency is achieved. Also when an amidecompound described above is employed as a nucleating agent, anadvantageously excellent rigidity is achieved.

In this invention, a nucleating agent and various desirable additivesare dry-blended using a mixer such as Henschel mixer. Alternatively, akneading may be effected using a single- or twin-screw extruder, Banburymixer and the like. When a high melting polymer is used as a nucleatingagent, the high melting polymer may be added to a reactor simultaneouslyor sequentially during the production of a propylenic polymer. Additivesemployed if necessary are antioxidant, neutralizing agent,slipperiness-imparting agent, anti-blocking agent, anti-frosting agentand antistatic agent and the like.

The amount of a nucleating agent added in the invention is 10 ppm orhigher, preferably 10 to 10000 ppm, more preferably to 5000 ppm,particularly 10 to 2500 ppm, based on a propylenic polymer [1], apropylene homopolymer [a] or a propylenic copolymer [a′]. An amount lessthan 10 ppm provides no improvement in the moldability, while an amountexceeding 10000 ppm fails to exhibit corresponding increase in theeffect.

[3] Molded Article

A molded article in this invention is a molded article obtained bymolding a propylenic polymer [1], a propylene homopolymer [a] or apropylenic copolymer [a′] described above (hereinafter also referred toas inventive propylenic polymers). An inventive molded article has asoftness (also referred to as pliability) and a high % elasticityrecovery (ability of recovery after being stretched), and ischaracterized by a less stickiness in spite of its high softness, i.e.,a low modulus, as well as an excellent transparency.

A molded article in this invention may for example be films, sheets,containers, automobile interior parts, electricity power line housingsand the like. Films may for example be films for food product packagingsand films for agricultural uses (such as for green houses). Containersmay for example be clear cases, clear boxes, decorated boxes utilizingtheir excellent transparency.

A molded article may be produced by injection molding, compressionmolding, injection stamping, gas-assisted injection molding, extrusionmolding, blow molding and the like.

The molding conditions may not particularly be limited, provided that atemperature capable of allowing a resin to be molten and to flow isemployed, and in this context, the description in the second inventioncan analogously be applied. The film may be oriented or may not beoriented. When oriented, it is preferred to be biaxially oriented. Thebiaxially orienting conditions involve the parameters described in thesecond invention.

A film may be surface-treated if necessary to enhance its surface energyor to impart the surface with a polarity.

To a film, a customary additives such as antioxidant, neutralizingagent, slipperiness-imparting agent, anti-blocking agent, anti-frostingagent, antistatic agent and the like may be incorporated as desired.

A film further containing an inorganic microparticle such as talcexhibits an excellent slipperiness, which leads to an improvement insecondary processing performances such as bag making or printingperformance, due to which it is suitable as a general-purpose packagingfilm subjected to a high speed machine including various automaticfilling-packaging laminators.

A film produced by molding a propylenic polymers containing adibenzylidene sorbitol or its derivative as a nucleating agent has aparticularly excellent transparency which is highly display-oriented,and which makes it suitable as a package film of a toy or a stationery.

A film produced by molding a propylenic polymers containing an amidecompound as a nucleating agent has a particularly excellent rigidity andexhibits a less problematic wrinkling when being wound during a highspeed bag making, due to which it is suitable as a general-purposepackaging film subjected to a high speed bag making machine.

An inventive propylenic polymers are used preferably also as propylenicresin modifiers.

[IV] Fourth Invention

The fourth invention consisting of a propylenic resin composition [1], amethod for producing the same [2], and a molded article [3] is detailedbelow.

[1] Propylenic Resin Composition

A propylenic resin composition in this invention consists of a propylenehomopolymer (a) and/or a propylenic copolymer (a′), and is a resincomposition (hereinafter also referred to as a propylenic resincomposition of the first invention] which satisfies the followingrequirements [1] to [3]:

[1] the amount of the components extracted with a boiling diethyletherranges 1 to 99% by weight;[2] in a propylene homopolymer (a), a component extracted with a boilingdiethylether satisfies the following requirements (1) to (3):(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight; and,[3] in a propylenic copolymer (a′), a component extracted with a boilingdiethylether satisfies the following requirements (4) and (5):(4) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(5) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

A propylene homopolymer (a) and a propylene copolymer in this inventionare as described below.

(a) Propylene Homopolymer

A propylene homopolymer in this invention is a polymer which satisfiesthe following requirements (1) to (3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

By satisfying the requirements described above, an inventive propylenehomopolymer provides a molded article exhibiting well-balanced amount ofthe stickiness-imparting components, low modulus and transparency. Thus,it exhibits a low modulus and an excellent softness (referred to aspliability), contains a reduced amount of a stickiness-impartingcomponent and has an excellent surface characteristics (for examplethose experienced as a less bleeding and a less migration of astickiness-imparting component into other products), and is alsoassociated with an advantageously excellent transparency.

A % meso-pentad (% mmmm) employed in the present invention and a %racemi-pentad (% rrrr) are the same to those discussed in the firstinvention. A meso-pentad fraction (mmmm) of an inventive propylenehomopolymer less than 20% by mole may cause a stickiness. One exceeding60% by mole may represent disadvantageously high modulus. A value of[rrrr/(1−mmmm)] of an inventive propylene homopolymer which exceeds 0.1may cause a stickiness.

A ¹³C-NMR spectrum is obtained similarly as in the first invention.

A propylene homopolymer in this invention has an amount of thecomponents which are dissolved out at 25° C. or lower (W25) in atemperature-raising chromatography ranging from to 100% by weight. Morepreferably, such amount ranges from 30 to 100% by weight, and most:preferably 50 to 100% by weight. The description with regard to W 25 issimilar to those in the second invention.

In this invention, a propylenic homopolymer described above is furtherpreferred when it satisfies, among the requirements described above, thefollowing requirements:

(4) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 30 to 50% by mole;(5) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.08

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(6) the amount of the components which are dissolved out at 0° C. orlower (W25) in a temperature-raising chromatography ranges from 30 to100% by weight; and is particularly preferred when it satisfies thefollowing requirements:(7) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.06

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(8) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 50 to100% by weight.

A propylene homopolymer according to the invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with an Mw/Mn of 3.5 or less and/or a [η] of 1.0 to 5.0 dl/g beingmore preferred and an Mw/Mn of 3 or less and/or a [η] of 1.0 to 3.0 dl/gbeing particularly preferred. A molecular weight distribution (Mw/Mn)exceeding 4 may cause a stickiness, and an intrinsic viscosity [η] lessthan 0.5 dl/g may also cause a stickiness. A [η] exceeding 15.0 dl/gresults in a reduced flowability which may lead to a poor moldingperformance.

An Mw/Mn described above may be understood similarly as in the firstinvention.

In addition to the requirements, described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/gr. or less allows an inventivepropylene homopolymer to be more pliable and thus be more preferred. Avalue of ΔH is an index for the softness, and a higher value representsa higher modulus and a reduced softness. A ΔH is a fusion endothermiccalorie obtained using a differential scanning calorimeter(Perkin-Elmer, DSC-7) by fusing 10 mg of a sample for 3 minutes at 230°C. under a nitrogen atmosphere followed by lowering the temperature to0° C. at the rate of 10° C./minutes, followed by holding at 0° C. for 3minutes, and followed by raising the temperature at the rate of 10°C./minutes.

While an inventive propylene homopolymer may have or may not have amelting point (Tm) and a crystallization temperature (Tc), it ispreferred for the purpose of the softness that such values do not existor do exist only as low values, with a Tm not higher than 100° C. beingpreferred. The values of Tm and Tc are determined similarly as in thefirst invention.

While during an ordinary propylene polymerization process a 1,2insertion polymerization, which means that a carbon atom of a propylenemonomer on the side of a methylene undergoes a binding with an activecenter of a catalyst followed by a successive coordination of thepropylene monomers in the same manner whereby effecting thepolymerization, takes place generally, a 2,1 insertion or a 1,3insertion may also take place at a less incidence (sometimes referred toas abnormal insertion). In a homopolymer according to the invention, itis preferable that the incidence of such 2, 1 or 1,3 insertion is low.It is also preferable that these insertion rates satisfy therelationship represented by the following formula (1):

[(m−2,1)+(r−2,1)+(1,3)]≦5.0  (1)

wherein (m−2,1) is a % meso-2,1 insertion content determined by ¹³C-NMR,(r−2,1) is a % racemi-2,1 insertion content determined by ¹³C-NMR, and(1,3) is a % 1,3 insertion content determined by ¹³C-NMR, and, morepreferably, they satisfy the relationship represented by the followingformula (2):

[(m−2,1)+(r−2,1)+(1,3)]≦1.0  (2)

It is particularly preferred that they satisfy the relationshiprepresented by the following formula (3):

[(m−2,1)+(r−2,1)+(1,3)]≦0.1  (3).

When the relationship represented by Formula (1) is not satisfied, thecrystallinity is reduced far more than expected, and a stickiness mayarise.

(m−2, 1), (r−2, 1) and (1,3) are understood similarly as in the firstinvention.

A propylene homopolymer of she invention preferably exhibitssubstantially no peaks in a ¹³C-NMR spectrum which are assigned to amolecular chain terminal (n-butyl group) as a result of a 2,1 insertion.With regard to this molecular chain terminal as a result of a 2,1insertion, each % insertion content is calculated from the integratedintensity of each peak after assignment of the peak in the ¹³C-NMRspectrum in accordance with the report by Jungling et al (J. Polym.Sci.: Part A: Polym. Chem., 33, p 1305 (1995)).

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylene homopolymer in the invention to be furtherpreferred. A % boiling diethylether extract can be determined by themethod similar to that described in the first invention.

In addition to the requirements described above, a tensile elasticmodulus of 100 MPa or less, more preferably 70 MPa or less is associatedwith an inventive propylene homopolymer.

(a′) Propylenic Copolymer

A propylenic copolymer in this invention is a copolymer of propylene andethylene and/or an α-olefin having 4 to 20 carbon atoms which satisfiesthe following requirements (1) to (2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at 0° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

By satisfying the requirements described above, an inventive propyleniccopolymer provides a molded article exhibiting well-balanced amount ofthe stickiness-imparting components, low modulus and transparency. Thus,it exhibits a low modulus and an excellent softness (referred to aspliability), contains a reduced amount of a stickiness-impartingcomponent and has an excellent surface characteristics (for examplethose experienced as a less bleeding and a less migration of astickiness-imparting component into other products), and is alsoassociated with an advantageously excellent transparency. Astereoregularity index (P) in the invention is a value obtained bydetermining a ¹³C-NMR spectrum and then calculating a % meso-triad (mm)of a propylene chain similarly as in the first invention. An increase inthis value is associated with a higher stereoregularity. A propyleniccopolymer according to the invention preferably has a stereoregularityindex (P) of 65 to 80% by mole. A stereoregularity index (P) less than55% by weight results in a too reduced modulus, which may lead to a poormolding performance. At 90% by mole or higher, a softness is lost. It isfurther preferred that the W25 is 30 to 100% by weight, with 50 to 100%by weight being particularly preferred. A W25 less than 20% by weightresults in a loss of pliability. The meanings and the determinationmethod of a W25 are as described above.

A propylenic copolymer according to the invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with an (Mw/Mn) of 3.5 or less and/or a [η] of 1.0 to 5.0 dl/gbeing more preferred and an (Mw/Mn) of 3 or less and/or a [η] of 1.0 to3.0 dl/g being particularly preferred. A molecular weight distribution(Mw/Mn) exceeding 4 may cause a stickiness. An intrinsic viscosity [η]less than 0.5 dl/g may also cause a stickiness, and one exceeding 15.0dl/g results in a reduced flowability which may lead to a poor moldingperformance. The determination method of this Mw/Mn is as describedabove.

In addition to the requirements described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/gr. or less allows an inventivepropylenic copolymer to be more pliable and thus be more preferred.While a melting point (Tm) and a crystallization temperature (Tc) mayexist or may not, it is preferred for the purpose of the softness thatsuch values do not exist or do exist only as low values, with a Tm nothigher than 100° C. being preferred. ΔH, Tm and Tc are obtained asdescribed above.

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylenic copolymer in the invention to be furtherpreferred. The boiling diethylether extract is determined as describedabove.

In addition, the tensile elastic modulus is preferably 100 MPa or less,more preferably 70 MPa or less.

In conjunction with a propylenic copolymer according to the invention,an α-olefin having 4 to 20 carbon atoms may for example be ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene andthe like, and, in the invention, these may be employed alone or incombination with each other.

A propylenic copolymer according to the invention is preferably a randomcopolymer. The structural unit derived from propylene exists preferablyat a level of 90% by mole or higher, more preferably 95% by mole orhigher.

(2) Propylenic Resin Composition

A propylenic resin composition in this invention consists of 1 to 99% byweight of a propylenic polymer [I] and 99 to 1% by weight of apolyolefin [II] in which said propylenic polymer [I] satisfies thefollowing requirements (1) to (3):

(1) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140).

A propylenic polymer [I] in this invention is discussed first. Bysatisfying the requirements described above, an inventive propylenicpolymer [I] provides a molded article exhibiting well-balanced amount ofthe stickiness-imparting components, low modulus and transparency. Thus,it exhibits a low modulus and an excellent softness (referred to aspliability), contains a reduced amount of a stickiness-impartingcomponent and has an excellent surface characteristics (for examplethose experienced as a less bleeding and a less migration of astickiness-imparting component into other products), and is alsoassociated with an advantageously excellent transparency.

The requirements described above are discussed below. A propylenicpolymer in this invention has an amount of the components which aredissolved out at 25° C. or lower (W25) in a temperature-raisingchromatography which ranges from 20 to 100% by weight. Such amount ispreferably 30 to 100% by weight, more preferably 50 to 100% by weight.In this invention, a value of W25 less than 20% by weight results in adisadvantageous loss of pliability. The meanings and the determinationmethod of a W25 are as described above. Also in a propylenic polymer inthis invention, the amount of the components which are dissolved outinto hexane at 25° C. (H25) ranges from 0 to 80% by weight. Preferably,it is 0 to 50% by weight, particularly 0 to 25% by weight. H25 can beunderstood as described in the second invention. With a level of H25exceeding 80% by weight, a stickiness-imparting component exists in alarge amount, which may cause problematic blocking and transparencycharacteristics, because of which the use in a food or medical productis not acceptable.

Also in an inventive propylenic polymer, no melting point (Tm(° C.)) isobserved in DSC or, when any Tm is observed then the Tm and the fusionendothermic calorie ΔH(J/gr.) are in the relationship represented by thefollowing formula:

ΔH≧6×(Tm−140);

preferably by the following formula:

ΔH≧3×(Tm−120); and,

particularly by the following formula:

ΔH≧2×(Tm−100).

Tm and ΔH can also be understood similarly as in the second invention.

A propylenic polymer [I] in this invention is not particularly limited,provided that it can satisfy the requirements described above, and mayfor example be a propylene homopolymer or a propylenic copolymer.Specifically, a propylenic polymer [I] in this invention described abovecan more preferably be embodied by a propylene homopolymer (a) or apropylene copolymer (a′) described below.

A polyolefin [II] in this invention is discussed further later.

(3) Propylenic Resin Composition

A propylenic resin composition in this invention consists of 1 to 99% byweight of a propylene homopolymer (a) and 99 to 1% by weight of apolyolefin [II] in which said propylene homopolymer (a) satisfies thefollowing requirements (1) to (3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mnmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

A propylene homopolymer (a) in this invention is understood as describedabove.

A polyolefin [II] in this invention is discussed further later.

(4) Propylenic Resin Composition

A propylenic resin composition in this invention consists of 1 to 99% byweight of a propylenic copolymer (a′) and 99 to 1% by weight of apolyolefin [II] in which said propylenic copolymer (a) satisfies thefollowing requirements (1) to (2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

A propylenic copolymer (a′) in this invention is understood as describedabove.

A polyolefin [II] in this invention is discussed further later.

A propylene homopolymer (a) and a propylenic copolymer (a′) in thesections (2) to (4) described above may for example be produced by thefollowing method.

[Method for Producing Propylene Homopolymer (a) and Propylenic Copolymer(a′)]

A method for producing a propylene homopolymer (a) and a propyleniccopolymer (a′) according to the invention may be a method in which acatalyst system called a metallocene catalyst is used to homopolymerizepropylene or to copolymerize propylene and ethylene and/or an α-olefinhaving 4 to 20 carbon atoms. A metallocene catalyst may for example bethose described in the second invention. In the invention, amongmetallocene catalysts, one derived from a transition metal compoundwhose ligand forms a crosslinking structure via a crosslinking group ispreferred, and a particularly preferred method involves a multi-steppolymerization process comprising at least a step in which propylene ishomopolymerized, or propylene and ethylene and/or an α-olefin having 4to 20 carbon atoms are copolymerized in the presence of a metallocenecatalyst obtained by combining a transition metal compound whosecrosslinking structure is formed via 2 crosslinking groups with apromoter.

Typically, a catalyst consists of the following components.

(A) a transition metal compound(B) a component (B-1) which is a compound capable of forming an ioniccomplex by reacting with a transition metal compound as a component (A)and a component (B-2) which is an aluminoxane.

In addition to a component (A) and a component (B), an organic aluminiumcompound can be used as a component (C).

Components (A), (B) and (C) are similar to those described in the firstinvention, and each of components (B) and (C) may be used alone or incombination of two or more. The amount of each component to be used isalso similar to that employed in the first invention.

In a production method according to the invention, components (A), (B)and (C) may be subjected to a preliminary contact. Such preliminarycontact may be performed in a manner similar to that described in thefirst invention.

In the present invention, at least one of the catalyst components may beemployed as being supported on a suitable carrier. A carrier employed issimilar to that in the first invention. A method for allowing at leastone of the catalyst components to be supported on a carrier is alsosimilar to that in the first invention.

In the present invention, a catalyst may be prepared by irradiating adynamic wave upon contact between components (A), (B) and (C). Suchelastic wave is usually a sound wave, preferably an ultrasonic wave.Typically, an ultrasonic wave at a frequency of 1 to 1000 kHz,preferably 10 to 500 kHz may be exemplified.

A catalyst thus obtained may be used in a polymerization after beingisolated as a solid by distilling a solvent off, or alternatively it maybe subjected directly to a polymerization.

As is discussed already in the second invention, a catalyst may beproduced by allowing at least one of a component (A) and a component (B)to be supported on a carrier within the system of polymerization.

Also in this invention, as is discussed already in the first invention,a catalyst may be produced by allowing at least one of a component (A)and a component (B) to be supported on a carrier within the system ofpolymerization.

The ratio of each component to a carrier is also the same to thatemployed in the first invention. The polymerization catalyst of theinvention thus prepared usually has a mean particle size of 2 to 200 μm,preferably 10 to 150 μm, particularly 20 to 100 μm, and a specificsurface area usually of 20 to 1000 m²/g, preferably 50 to 500 m²/g. Inan inventive catalyst, the amount of a transition metal in 100 g of acarrier is usually 0.05 to 10 g, preferably 0.1 to 2 g. An amount of atransition metal departing from the range described above may result ina reduced activity.

A propylenic polymer employed in this invention can be produced using apolymerization catalyst described above by homopolymerizing a propyleneor by copolymerizing propylene and ethylene and/or an α-olefin having 4to 20 carbon atoms.

In such procedure, a polymerization method is not particularly limitedand may be a slurry polymerization, a vapor phase polymerization, a bulkpolymerization, a solution polymerization, a suspension polymerizationand the like, and those particularly preferred are a slurrypolymerization and a vapor phase polymerization.

A polymerization condition involves a polymerization temperature usuallyof −100 to 250° C., preferably −50 to 200° C., more preferably 0 to 130°C. The ratio of a catalyst to a reactant, represented as startingmonomer/component (A) (molar ratio), is preferably 1 to 10⁸,particularly 100 to 10^(s). A polymerization time usually of 5 minutesto 10 hours, and a reaction pressure preferably of atmospheric pressureto 200 kg/cm², particularly atmospheric pressure to 100 kg/cm areemployed.

The molecular weight of a polymer may be adjusted by appropriatelyselecting the type and the amount of each catalyst component and thepolymerization temperature, or by performing the polymerization in thepresence of hydrogen.

When a polymerization solvent is employed, the types of the solvents maybe similar to those in the first invention. A monomer such as anα-olefin may also be employed as a solvent. Some polymerization methodsneed no use of solvents.

Upon polymerization, a polymerization catalyst described above may beused to perform a preliminary polymerization. Such preliminarypolymerization may be similar to that in the first invention.

On the other hand, a polyolefin [II] in the sections (2) to (4)described above is one which is detailed below.

A polyolefin [II] in this invention is not particularly limited, and maybe a homopolymer of an olefin or a copolymer of two or more olefins aswell as mixtures thereof. A component [II] is preferably a propylenicpolymer (b) having a crystallization temperature (Tc(° C.)) in whichTc≧0° C., and/or an olefin polymer (b′) having a glass transitiontemperature (Tg(° C.)) in which Tg≦10° C.

(b) Propylenic Polymer

A propylenic polymer (b) having a crystallization temperature (Tc(° C.))in which Tc≧0° C. may for example be a general-purpose polypropylene.Such general purpose polypropylene may for example be a propylenehomopolymer (1) and a propylenic copolymer (2).

(1) Propylene Homopolymer

As a propylene homopolymer, a high stereoregular isotactic polypropyleneis preferred. Typically, one having a % isotactic pentad, which is anindex for a stereoregularity, of 85% by mole or higher, more preferably90% by mole or higher, and particularly 95% mole or higher. In thiscontext, a % isotactic pentad is a % isotactic moiety in a triad unitdetermined by ¹³C-NMR, and is a value obtained as a ratio of the signalintensity of 21.7 to 22.5 ppm to the total signal intensity of 19.8 to22.5 ppm. ¹³C-NMR is determined as described above.

(2) Propylenic Copolymer

A propylenic copolymer may for example be a random polypropylene or ablock polypropylene obtained by copolymerizing propylene and ethylene oran α-olefin having 4 to 20 carbon atoms. An α-olefin having 4 to 20carbon atoms may for example be an α-olefin which is straight, branched,or substituted with an aromatic ring. Those exemplified typically are astraight monoolefin such as 1-hexene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene and the like, a branched monoolefin such as3-methylbutene-1,3-methylpentene-1,4-methylpentene-1,2-ethylhexene-1,2,2,4-trimethylpentene-1and the like, and a monoolefin substituted with an aromatic ring such asstyrene. Each α-olefin may be employed alone or in combination with twoor more.

A propylenic copolymer preferably has a high stereoregularity of apropylene chain moiety. A stereoregularity index of the propylene chainmoiety of 90% or higher is more preferred. A higher crystallinity inspite of a low melting point is further preferred. These characteristicsare associated for example with a propylenic polymer whosecrystallization temperature Tc is elevated as a result of the additionof a nucleating agent.

Examples of a propylenic copolymer are an ethylene/propylene copolymer,an ethylene/1-butyne/propylene copolymer, 1-butene/propylene copolymerand the like.

Ethylene/propylene copolymers which are employed preferably are thosedescribed in JP-A-10-130336 and JP-A-10-142431. Thus, a preferableethylene/propylene copolymer satisfies the following requirements [1] to[6]:

[1] The ethylene unit content (X(wt %)) in a copolymer is 0.2 to 15 wt%;[2] The melt index (MI (g/10 min) of a copolymer is 0.1 to 15 g/10 min;[3] The boiling diethylether extract (Ext (wt %)) and X are in therelationship represented the formula (1) or (2):

Ext≧0.2Ω+1.0 (0.2≦Ω≦5)  (1)

Ext≦2.0 (5≦Ω<15)  (2);

[4] The melting point (Tm(° C.)) determined by a differential scanningcalorimeter and x are in the relationship represented by the formula (3)or (4):

Tm≦140 (0.2≦Ω<4)  (1)

Tm≦160−5Ω (4≦Ω<15)  (4);

[5] The % isotactic triad (mm (mol %)) of a PPP chain moiety determinedby ¹³C-NMR is 90% by mole or higher; and,[6] The % PEP chain moiety (R(mol %)) determined by ¹³C-NMR and Ω are inthe relationship represented by the formula (5):

R≧0.5Ω+1  (5).

The meanings and the method for determination of each variant are inaccordance with the descriptions of the publications listed above.

An ethylene/1-butene/propylene copolymer which is employed preferably isone described in JP-A-11-60639. Thus, it is a copolymer of propylene,ethylene and 1-butene and is a propylenic random copolymer whichsatisfies the following requirements [1] to [6]:

[1] The ethylene unit content in a copolymer (α mol %) and the 1-buteneunit content (β mol %) are in the relationship represented by theformula (1):

4≦α+β≦15  (1);

[2] The melt index of a copolymer (MI (g/10 min) is 1 to 12 g/10 min;[3] The boiling diethylether extract (E) and (α+β) are in therelationship represented by the formula (2) when (α+β)≦12 and by theformula (3) when (α+β)>12:

E≧0.2(α+β)+0.6  (2)

E≦3.0  (3)

[4] The melting point (Tm(° C.)) determined by a differential scanningcalorimeter and (α+β) are in the relationship represented by the formula(4):

Tm≦164−3.6(α+β)  (4)

[5] The stereoregularity index P (mol %) determined by ¹³C-NMR is 98% bymole or higher; and,[6] The ratio (Mw/Mn) of the weight mean molecular weight (Mw) to thenumber mean molecular weight (Mn) determined by a gel permeationchromatography (GPC) is 6 or less.

A method for producing a propylene homopolymer (1) or a propyleniccopolymer (2) described above is not particularly limited, and variousolefin polymerization catalyst may be employed in the production. Forexample, a highly active Ziegler-Natta catalyst comprising a catalystcomponent obtained by bringing a carrier such as a magnesium compoundand a compound of a transition metal of Group IV in the periodic tableinto contact in the presence or absence of an electron donor and anorganic aluminium compound (JP-A-53-43094, JP-A-55-135102,JP-A-55-135103, JP-A-56-18606 and the like), or a catalyst called ametallocene catalyst (JP-A-58-19309, JP-A-2-167307 and the like) may beemployed.

A highly active Ziegler-Natta catalyst may for example be a catalystobtained by bringing the following components:

(A) a solid titanium catalyst comprising:a. titanium;b. magnesium; and,c. an electron donor;and,(B) an organic aluminium compound, optionally together with (C) anorganic silane compound into contact. Alternatively, a catalyst obtainedby subjecting the catalyst described above to a preliminarypolymerization with olefins followed by bringing into contact with anorganic aluminium compound optionally together with (C) an organicsilane compound may be exemplified.

A metallocene catalyst which may be exemplified as a preferred exampleis a metallocene catalyst disclosed in JP-A-10-260376. Thus, an olefinpolymerization catalyst obtained by bringing at least an aluminoxaneinto contact with a compound of a transition metal of Groups IV to VI inthe periodic table optionally with an organic aluminium compound may beexemplified. In addition, an olefin polymerization catalyst may forexample be an olefin polymerization catalyst in which at least one ofthe catalyst component is supported on a carrier. A compound of atransition metal of Groups IV to VI in the periodic table is preferablyone represented by any of the following formulae (1) to (3):

Q¹a(C₅H_(5-a-b)R¹⁶ _(b))(C₅H_(5-a-c)R¹⁷ _(c))M²X³ _(p)Y³ _(q)  (1)

Q²a(C₅H_(5-a-d)R¹⁸ _(d))Z¹M²X³ _(p)Y³ _(q)  (2)

M²X⁴ _(r)  (3)

Wherein Q¹ denotes a binding group which crosslinks two conjugate5-membered ring ligands (C₅H_(5-a-b)R¹⁶ _(b)) and (C₅H_(5-a-c)R¹⁷ _(c)),Q² denotes a binding group which crosslinks a conjugate 5-membered ringligand (C₅H_(5-a-d)R¹⁸ _(d)) and Z¹ group; each of R¹⁶, R¹⁷ and R¹⁸ is ahydrocarbon group, a halogen atom, an alkoxy group, a silicon-containinghydrocarbon group, a phosphorus-containing hydrocarbon group, anitrogen-containing hydrocarbon group or a boron-containing hydrocarbongroup, and a is 0, 1 or 2; each of b, c and d is an integer of 0 to 5when a=0, an integer of 0 to 4 when a=11, and an integer of 0 to 3 whena=2; p+q=the valency of M²−2, r=the valency of M²; M² denotes atransition metal of Groups IV to VI in the periodic table; each of X³,Y³ and Z¹ denotes a covalent-binding or ionic-binding ligand, X⁴ is acovalent-binding ligand; or, X³ and Y³ may be taken together to form acyclic structure.(b′) Olefin Polymer

An olefin polymer (b′) having a glass transition temperature (Tg(° C.))in which Tg≦−10° C. in a polyolefin [II] may for example be an ethylenicpolymer. Such ethylenic polymer is not particularly limited providedthat it contains at least an ethylene component. Such ethylenic polymermay for example be a high density polyethylene, a low densitypolyethylene, a linear low density polyethylene, an ethylene-α-olefincopolymer and the like.

A preferred ethylene-α-olefin copolymer satisfies the followingrequirements (1) to (3).

(1) α-Olefin

An α-olefin employed in an ethylene-α-olefin copolymer may for examplebe a straight, branched or aromatic ring-substituted α-olefin having 3to 18, preferably 6 to 18, particularly 6 to 18 carbon atoms. A numberof carbon atoms less than 6 results in a reduced tensile elongation atbreak, which may leads to an elevated brittleness temperature. Anα-olefin having 3 to 18 carbon atoms may typically be a straightmonoolefin such as propylene, 1-butene, 1-hexene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene and the like, a branched monoolefinsuch as3-methylbutene-1,3-methylpentene-1,4-methylpentene-1,2-ethylhexene-1,2,2,2-trimethylpentene-1 and the like, as well as a monoolefinsubstituted with an aromatic ring such as styrene. Each α-olefin may beemployed alone or in combination with two or more.

(2) α-Olefin Content

The α-olefin content in an ethylene-α-olefin copolymer is 10 to 60% byweight, preferably 20 to 50% by weight. A content less than 10% byweight may result in a reduced impact strength. A content exceeding 60%by weight may result in a reduced rigidity of a resin composition.

(3) Characteristics of Ethylene-α-Olefin Copolymer 1) Melt Index (MI)

The melt index of an ethylene-α-olefin copolymer employed in thisinvention is 0.05 to 150 g/10 min, preferably 0.1 to 100 g/10 minutes,more preferably 1 to 70 g/10 minutes. A melt index less than 150 g/10minutes may result in a reduced impact strength. A measurement was inaccordance with JIS-K-7210 (determined with a load of 2160 g at 190°C.).

2) Maximum Melting Point (Tm(° C.))

The maximum melting point (Tm(° C.)) of an ethylene-α-olefin copolymeremployed in this invention is 90° C. or lower, preferably 85° C. orlower, more preferably 80° C. or lower. A Tm exceeding 90° C. may resultin a reduced impact strength. A measurement was conducted as follows.About 10 mg of a sample was heated for 3 minutes at 190° C. using adifferential scanning calorimeter (DSC-7: Perkin-Elmer) and then cooledslowly at 10° C./min to 25° C. to effect crystallization, and the sampletemperature was raised from 25° C. to 160° C. at the raising rate of 10°C./min to obtain a fusing curve. The highest temperature of the peakobtained in this procedure was regarded as the maximum melting point.

3) Weight Mean Molecular Weight/Number Mean Molecular Weight (Mw/Mn)

The weight mean molecular weight/number mean molecular weight (Mw/Mn) ofan ethylene-α-olefin copolymer is 3.0 or less, preferably 2.5 or less. Avalue exceeding 3.0 results in a reduced tensile elongation at break. Ameasurement was conducted as follows. A solution of 10 mg of sample in20 ml of 1,2,4-trichlorobenzene was supplemented with an antioxidant2,6-di-t-butyl-p-cresol (commonly referred to as BHT) at 0.1 w/v % andheated at 150° C. in a conical flask and then stirred for 1 hour toeffect dissolution. This solution was subjected to a gel permeationchromatography using a device manufactured by Waters (model: 150°C.-ALC/GPC) and the weight mean molecular weight (Mw) and the numbermean molecular weight (Mn) were calculated as being converted to thevalues of a standard polystyrene having a known molecular weight(Mono-distributed polystyrene manufactured by TOSO), whereby obtainingthe value of Mw/Mn of the sample. The column TOSO GMH6-HT was used withthe sample injection volume of 400 μl at the flow rate of 1.0 ml/min at135° C.

A method for producing an ethylene-α-olefin copolymer is notparticularly limited, and various olefin polymerization catalysts may beemployed in the production. For example, an olefin polymerizationcatalyst disclosed in JP-A-9-87479 can be employed.

While an inventive propylenic resin composition [I] is embodied moretypically by a resin composition in which a propylene homopolymer (a)and/or a propylenic copolymer (a′) described above is combined with apolyolefin [II] described above at a weight ratio of 1:99 to 99:1, aninventive propylenic resin composition [I] may be supplemented with anucleating agent. Such nucleating agent may typically be any of thosedescribed in the first invention.

In this invention, the use of an inorganic microparticle such as talc asdescribed above as a nucleating agent results in an excellentslipperiness of a molded film and provides an improvement in thecharacteristics such as printability.

An inventive propylenic resin may be mixed with a nucleating agent andvarious desirable additives by means of a dry-blending using a mixersuch as Henschel mixer. Alternatively, a kneading may be effected usinga single- or twin-screw extruder, Banbury mixer and the like. When ahigh melting polymer is used as a nucleating agent, the high meltingpolymer may be added to a reactor simultaneously or sequentially duringthe production of a propylenic polymer. Additives employed if necessaryare antioxidant, neutralizing agent, slipperiness-imparting agent,anti-blocking agent, anti-frosting agent and antistatic agent and thelike.

The amount of a nucleating agent added in the invention is 10 ppm orhigher, preferably 10 to 10000 ppm, more preferably to 5000 ppm,particularly 10 to 2500 ppm, based on a propylenic resin. An amount lessthan 10 ppm provides no improvement in the moldability, while an amountexceeding 10000 ppm fails to exhibit corresponding increase in theeffect.

[2] Method for Producing Propylenic Resin Composition

A method for producing an inventive propylenic resin composition [1] istypically a blending of a propylene homopolymer (a) and/or a propyleniccopolymer (a′) with a polyolefin [II] described above. A procedure forblending may for example be a powder blending method using a kneader. Akneader may be Banbury mixer and a twin-screw kneader and the like. Areactor blending method in which a blending is effected in apolymerization reaction vessel may also be employed. Preferably, areactor blending method capable of blending each component sufficientlyis employed.

A reactor blending method may be a multi-step polymerization in whichtwo or more polymerization steps are employed or a polymerization methodin which a co-catalyst comprising two or more transition metal compoundsis employed (also referred to as a multi-stage polymerization). Suchmulti-step polymerization may for example be a polymerization methodcomprising at least a step for producing a propylenic resin [1]described above, i.e., a polymerization step employing at least a lowstereoregular metallocene catalyst. A low stereoregular metallocenecatalyst means a metallocene catalyst which provides a component (a) or(a′) described above. Representatives are the catalysts exemplified asthe catalysts for producing a component (a) or (a′) described above. Amulti-step polymerization may for example be a multi-step sequentialpolymerization employing a high activity-supporting Ziegler-Nattacatalyst and a low stereoregular metallocene catalyst or a multi-stepsequential polymerization employing a high stereoregular metallocenecatalyst and a low stereoregular metallocene catalyst. A preferred highactivity-supporting Ziegler-Natta catalyst is a high activity-supportingZiegler-Natta catalyst capable of providing a polypropylene having ameso-pentad fraction (mmmm) exceeding 60% by mole, and those listedabove are exemplified typically. A high stereoregular metallocenecatalyst means a metallocene catalyst capable of providing apolypropylene having a meso-pentad fraction (mmmm) exceeding 60% bymole. Examples of a high stereoregular metallocene catalyst are, aslisted above, those described in JP-A-58-19309, JP-A-61-130314,JP-A-3-163088, JP-A-4-300887, JP-A-4-211694, JP-W-1-502036 and the like,such as a catalyst derived from a transition metal compound having, asits one or two ligands, cyclopentadienyl group, substitutedcyclopentadienyl group, indenyl group, substituted indenyl group and thelike or and a transition metal compound in which said ligands arecontrolled geometrically in combination with a promoter.

A polymerization method employing a co-catalyst may for example be apolymerization method employing a co-catalyst at least one component ofwhich consists of a low stereoregular metallocene catalyst. One whichcan be exemplified is a polymerization method employing a co-catalystcomprising a high stereoregular metallocene catalyst and a lowstereoregular metallocene catalyst. A co-catalyst may be supported on acarrier. One which can be exemplified is a polymerization methodemploying a co-supported-catalyst obtained by allowing a highstereoregular metallocene catalyst and a low stereoregular metallocenecatalyst to be supported on a carrier. A low stereoregular metallocenecatalyst may be a metallocene catalyst which provides a component (a) or(a′) described above.

Among those described above, a polymerization method employing aco-catalyst is preferred as an inventive production method, and apolymerization method employing a co-supported-catalyst is particularlypreferred.

[3] Molded Article

A molded article in this invention is a molded article obtained bymolding a propylenic resin composition [1] described above. An inventivemolded article has a softness (also referred to as pliability)

And is characterized by a less stickiness in spite of its high softness,and is excellent also in terms of heat resistance. An inventive moldedarticle is pliable and has a high % elasticity recovery (ability ofrecovery after being stretched), and is excellent also in terms of lowtemperature impact resistance, with such characteristics beingwell-balanced.

A molded article in this invention may for example be films, sheets,fibers, containers, automobile interior parts, housings of home electricdevices. Films may for example be films for food product packagings andfilms for agricultural uses (such as for green houses). Containers mayfor example be cases, boxes, decorated boxes and the like.

A propylenic resin composition according to the invention is suitable toan extrusion molded article, particularly as a film and a sheet. Suchfilm and sheet may be laminated. Since an inventive propylenic resincomposition is characterized also by its broad composition distributionwhich allows the molding temperature range upon orientation to be widerand the moldability to be improved, it is applied preferably also to anoriented film and a fiber and the like.

A method for molding into an article may for example be an injectionmolding, compression molding, injection stamping, gas-assisted injectionmolding, extrusion molding, blow molding, calendering and the like. Amolding method employing an inventive propylenic resin composition givesa broader composition distribution which leads to an improvedmoldability, and also provides a higher crystallization rate whenemploying a blending of a highly crystalline resin (resin having ahigher Tc), resulting in an improved molding cycle. Also in acalendering, a broader composition distribution allows the viscosity tobe less dependent on the temperature, resulting in an improvedmoldability.

The molding conditions may not particularly be limited, provided that atemperature capable of allowing a resin to be molten and to flow isemployed, and a usual case involves a resin temperature of 50° C. to300° C. and a mold temperature of 60° C. or lower.

When a film is formed as a molded article in this invention, a methodwhich may be employed includes ordinary compression molding, extrusionmolding, blow molding, cast molding and the like. The film obtained maybe oriented or may not be oriented. When oriented, it is preferred to bebiaxially oriented. The biaxially orienting conditions involve theparameters described below.

[1] Sheet Molding Conditions

Resin temperature of 50 to 200° C., chill roll temperature of 50° C. orlower

[2] Lengthwise Orienting Conditions

Orienting magnitude of 3 to 7 times, orienting temperature of 50 to 100°C.

[3] Widthwise Orienting Conditions

Orienting magnitude of 6 to 12 times, orienting temperature of 50 to100° C.

A film may be surface-treated if necessary to enhance its surface energyor to impart the surface with a polarity.

For example, corona discharge treatment, chromic acid treatment, flametreatment, hot gas treatment, ozone- or UV irradiation treatment may forexample be employed. The surface may be embossed by, for example,sand-blast method or solvent treatment.

To a film, a customary additives such as antioxidant, neutralizingagent, slipperiness-imparting agent, anti-blocking agent, anti-frostingagent, antistatic agent and the like may be incorporated as desired.

A film further containing an inorganic microparticle such as talcexhibits an excellent slipperiness, which leads to an improvement insecondary processing performances such as bag making or printingperformance, due to which it is suitable as a general-purpose packagingfilm subjected to a high speed machine including various automaticfilling-packaging laminators.

A film produced by molding a propylenic resin composition containing adibenzylidene sorbitol or its derivative as a nucleating agent has aparticularly excellent transparency which is highly display-oriented,and which makes it suitable as a package film of a toy or a stationery.

A film produced by molding a propylenic resin composition containing anamide compound as a nucleating agent has a particularly excellentrigidity and exhibits a less problematic wrinkling when being woundduring a high speed bag making, due to which it is suitable as ageneral-purpose packaging film subjected to a high speed bag makingmachine.

[V] Fifth Invention

The fifth invention consisting of a propylenic resin composition [1] anda film and a sheet made therefrom are detailed below.

[1] Propylenic Resin Composition

An inventive propylenic resin composition [1] consists substantially ofa propylene homopolymer and/or a propylenic copolymer, and a resincomposition having a peak top temperature (Tc(° C.)) on the side of themaximum temperature on a crystallization curve and a differentialcalorie (ΔHm(J/g)) on a fusion curve, as determined by a differentialscanning calorimeter (DSC), which are in the relationship represented bythe following formula:

Tc≧(1/4)·ΔHm+90  (1-1)

and having a frequency (w (rad/sec)) at which the storage modulus(G′(Pa)) and the loss elasticity (G″(Pa)) based on the frequencydistribution determination of the melt viscoelasticity become equal toeach other and a ΔHm, which are in the relationship represented by thefollowing formula:

ω≦(1/10)·ΔHm+15  (2-1)

By satisfying the requirements described above, an inventive propylenicresin composition provides a film or sheet whose pliability andtransparency are excellent and whose heat seal strength is improvedsubstantially. For example, a film having a tensile elastic modulus of1000 MPa or less, a haze of 5% or less and a heat seal strength of 1000gf/15 mm or higher can be obtained. Especially with regard to the heatseal strength, a film having a far more excellent heat seal strengtheven at a high sealing temperature, e.g. at 160° C. or higher, canadvantageously be obtained. Another advantageous properties are a higherheat seal temperature and a higher heat resistance when compared withthose possessed by other propylenic resin composition having acomparable pliability.

In addition to a sheet or film, a laminated film or sheet formed bylamination or co-extrusion may preferably employ an inventive propylenicresin composition as at least one layer component thereof.

When the requirement (1-1) described above is not satisfied, thepliability of a resultant film or sheet is reduced, and the transparencyis also reduced. When the requirement (2-1) described above is notsatisfied, a resultant film or sheet fails to exhibit an improved heatseal strength or excellent transparency, although it has a certainpliability.

As a propylenic resin composition in this invention, a resin compositionsatisfying:

Tc≧(1/4)·ΔHm+92  (1-2); and,

ω≦(1/10)·ΔHm+13  (2-2),

is more preferred since it provides a film or sheet having excellentpliability and transparency as well as an improved seal strength.

A peak top temperature (Tc(° C.)) on the side of the maximum temperatureon a crystallization curve and a differential calorie (ΔHm(J/g)) on afusion curve as determined by a differential scanning calorimeter (DSC)in this invention are determined as described in the fourth invention. Afrequency (ω(rad/sec)) at which the storage modulus (G′(Pa)) and theloss elasticity (G″(Pa)) based on the frequency distributiondetermination of the melt viscoelasticity become equal to each other isdetermined by the procedure described below. Thus, a rotary rheometermanufactured by RIHEOMETRIX is used together with a cone plate (25 mm indiameter, 0.10 radian in cone angle) at the temperature of 175° C. withthe initial strain of 20% to perform the frequency distributiondetermination of the melt viscosity, and the storage modulus (G′(Pa)),the loss elasticity (G″(Pa)) and the frequency (co(rad/sec)) givingG′=G″ are determined. A complex modulus of elasticity G* (iω) at afrequency (C (rad/sec)) can be represented by a stress σ* and a strainγ* as shown below.

G*(iω)=σ*/γ*=G′(ω)+iG″(ω)

wherein i is an imaginary number unit.

A propylenic resin composition in this invention is not particularlylimited as far as the requirements described above are satisfied. Forexample, a propylenic resin composition comprising 1 to 99% by weight ofa propylenic polymer [I] satisfying the following requirements:

(1) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight;(2) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and,(3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm isobserved then the Tm and the fusion endothermic calorie ΔH(J/gr.) are inthe relationship represented by the following formula:

ΔH≧6×(Tm−140);

and 99 to 1% by weight of a crystalline propylenic polymer [II] may beexemplified.

By satisfying the requirements shown above, a propylenic polymer [I] inthis invention provides a resultant film or sheet whose amount of thestickiness-imparting components, low modulus and transparency arewell-balanced. Thus, it exhibits a low modulus and an excellent softness(referred to as pliability), contains a reduced amount of astickiness-imparting component and has an excellent surfacecharacteristics (for example those experienced as a less bleeding and aless migration of a stickiness-imparting component into other products),and is also associated with an advantageously excellent transparency.

The requirements described above to be satisfied by a propylenic polymer[I] in this invention are discussed below. In a propylenic copolymer [I]in this invention, the amount of the components which are dissolved outat 25° C. or lower (W25) in a temperature-raising chromatography rangesfrom 20 to 100% by weight. More preferably, such amount ranges from to100% by weight, and most preferably 50 to 100% by weight. W25 is anindex for the softness of a propylenic polymer [I]. An increase in thisvalue is associated with an increase in the component having a highermodulus and/or a broader stereoregularity distribution. In thisinvention, a value W25 less than 20% may result in a disadvantageousloss of the pliability. The meanings of W25 are as described in thesecond invention.

Also in a propylenic polymer [I] in this invention, the amount of thecomponents which are dissolved out into hexane at 25° C. (H25) rangesfrom 0 to 80% by weight. Preferably, it is 0 to 50% by weight,particularly 0 to 25% by weight. H25 can also be understood as describedin the second invention.

Also in an inventive propylenic polymer [I], no melting point (Tm(° C.))is observed in DSC or, when any Tm is observed then the Tm and thefusion endothermic calorie ΔH(J/g) are in the relationship representedby the following formula:

ΔH≧6×(Tm−140);

preferably by the following formula:

ΔH≧3×(Tm−120); and,

particularly by the following formula:

ΔH≧2×(Tm−100).

Tm and ΔH can also be understood similarly as in the second invention.

A propylenic polymer [I] in this invention is not particularly limited,provided that it can satisfy the requirements described above, and mayfor example be a propylene homopolymer or a propylenic copolymer.Specifically, a propylenic polymer [I] in this invention described abovecan more preferably be embodied by a propylene homopolymer [a] or apropylene copolymer [a′] described below.

[a] Propylene Homopolymer

A propylene homopolymer [a] in this invention is a polymer satisfyingthe following requirements (1) to (3):

(1) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 20 to 60% by mole;(2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.1

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(3) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

When a propylene homopolymer [a] in this invention satisfies therequirements described above, a resultant film or sheet exhibitswell-balanced amount of the stickiness-imparting components, low modulusand transparency. Thus, it exhibits a low modulus and an excellentsoftness (also referred to as pliability), contains a reduced amount ofa stickiness-imparting component and has an excellent surfacecharacteristics (for example those experienced as a less bleeding and aless migration of a stickiness-imparting component into other products),and is also associated with an advantageously excellent transparency.

A % meso-pentad (% mmmm) and a racemi-pentad fraction (rrrr) referred inthis invention are the same to those discussed in the first invention. Ameso-pentad fraction (mmmm) of an inventive propylene homopolymer [a]less than 20% by mole may cause a stickiness. One exceeding 60% by molemay represent disadvantageously high modulus. A value [rrrr/(1−mmmm)] ofa propylene homopolymer [a] in this invention which exceeds 0.1 causes astickiness. A ¹³C-NMR spectrum is obtained similarly as in the firstinvention. A W25 of an inventive propylene homopolymer [a] less than 20%results in the loss of pliability.

A propylenic homopolymer [a] described above is further preferred whenit satisfies, among the requirements described above, the followingrequirements:

(3) the meso-pentad fraction (mmmm (in percentage terms by mole)) rangesfrom 30 to 50% by mole;(4) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.08

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(6) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 30 to100% by weight; and is particularly preferred when it satisfies thefollowing requirements:(7) the meso-pentad fraction (mmmn (in percentage terms by mole)) rangesfrom 30 to 50% by mole;(8) the racemi-pentad fraction (rrrr) and (1−mmmm) are in therelationship represented by the following formula:

[rrrr/(1−mmmm)]≦0.06

wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction(mmmm) are not in percentage terms; and,(9) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 50 to100% by weight.

A propylene homopolymer [a] in this invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with an Mw/Mn of 3.5 or less and/or a [η] of 1.0 to 5.0 dl/g beingmore preferred and an Mw/Mn of 3 or less and/or a [η] of 1.0 to 3.0 dl/gbeing particularly preferred. A molecular weight distribution (Mw/Mn)exceeding 4 may cause a stickiness in a film or sheet. An intrinsicviscosity [η] less than 0.5 dl/g may also cause a stickiness, while thatexceeding 15.0 dl/g results in a gel or a fish eye in a film or sheet.

An Mw/Mn described above may be understood similarly as in the firstinvention.

In addition to the requirements described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/g or less allows an inventivepropylene homopolymer [a] to be more pliable and thus be more preferred.

In addition a propylene homopolymer [a] in this invention is furtherpreferred when it exhibits no crystallization peak in thecrystallization curve obtained by a differential scanning calorimetry(DSC).

While during an ordinary propylene polymerization process a 1,2insertion polymerization, which means that a carbon atom of a propylenemonomer on the side of a methylene undergoes a binding with an activecenter of a catalyst followed by a successive coordination of thepropylene monomers in the same manner whereby effecting thepolymerization, takes place generally, a 2,1 insertion or a 1,3insertion may also take place at a less incidence (sometimes referred toas abnormal insertion). In a homopolymer in this invention, it ispreferable that the incidence of such 2, 1 or 1,3 insertion is low. Itis also preferable that these insertion rates satisfy the relationshiprepresented by the following formula (1):

[(m−2,1)+(r−2,1)+(1,3)]≦5.0  (1)

wherein (m−2,1) is a % meso-2,1 insertion content determined by ¹³C-NMR,(r−2,1) is a % racemi-2,1 insertion content determined by ¹³C-NMR, and(1,3) is a % 1,3 insertion content determined by ¹³C-NMR, and, morepreferably, they satisfy the relationship represented by the followingformula (2):

[(m−2,1)+(r−2,1)+(1,3)]≦1.0  (2).

It is particularly preferred that they satisfy the relationshiprepresented by the following formula (3):

[(m−2,1)+(r−2,1)+(1,3)]≦0.1  (3).

When the relationship represented by Formula (1) is not satisfied, thecrystallinity is reduced far more than expected, and a stickiness mayarise.

(m−2, 1), (r−2, 1) and (1,3) are understood similarly as in the firstinvention.

A propylene homopolymer in this invention preferably exhibitssubstantially no peaks in a ¹³C-NMR spectrum which are assigned to amolecular chain terminal (n-butyl group) as a result of a 2,1 insertion.With regard to this molecular chain terminal as a result of a 2,1insertion, each % insertion content is calculated from the integratedintensity of each peak after assignment of the peak in the ¹³C-NMRspectrum in accordance with the report by Jungling et al (J. Polym.Sci.: Part A: Polym. Chem., 33, p 1305 (1995)).

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylene homopolymer [a] in the invention to befurther preferred. A % boiling diethylether extract can be determined bythe method similar to that described in the second invention.

In addition to the requirements described above, a tensile elasticmodulus of 100 MPa or less, more preferably 70 MPa or less is associatedwith an inventive propylene homopolymer [a].

[a′] Propylenic Copolymer

A propylenic copolymer [a′] in this invention is a copolymer ofpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atomswhich satisfies the following requirements (1) to (2):

(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and,(2) the amount of the components which are dissolved out at 25° C. orlower (W25) in a temperature-raising chromatography ranges from 20 to100% by weight.

By satisfying the requirements described above, an inventive propyleniccopolymer [a′] provides a film or sheet exhibiting well-balanced amountof the stickiness-imparting components, low modulus and transparency.Thus, it exhibits a low modulus and an excellent softness (referred toas pliability), contains a reduced amount of a stickiness-impartingcomponent and has an excellent surface characteristics (for examplethose experienced as a less bleeding and a less migration of astickiness-imparting component into other products), and is alsoassociated with an advantageously excellent transparency. Astereoregularity index (P) in the invention is a value obtained bydetermining a ¹³C-NMR spectrum using Nippon Densi Model JNM-EX400¹³C-NMR device under the conditions described in the first inventionfollowed by calculating a % meso-triad (mm) of a propylene chain. Anincrease in this value is associated with a higher stereoregularity. Apropylenic copolymer [a′] in this invention preferably has astereoregularity index (P) of 65 to 80% by mole. A stereoregularityindex (P) less than 55% by weight results in a too reduced modulus,which may lead to a poor molding performance. At 90% by mole or higher,a rigidness may arise and a softness is lost. It is further preferredthat the W25 is 30 to 100% by weight, with 50 to 100% by weight beingparticularly preferred. A W25 less than 20% by weight results in a lossof pliability. The meanings and the determination method of a W25 are asdescribed above.

A propylenic copolymer [a′] in this invention is preferred when itsatisfies, in addition to the requirements described above, that themolecular weight distribution (Mw/Mn) determined by a gel permeationchromatography (GPC) is 4 or less and/or the intrinsic viscosity [η]determined in a tetralin solvent at 135° C. ranges from 0.5 to 15.0dl/g, with an Mw/Mn of 3.5 or less and/or a [η] of 1.0 to 5.0 dl/g beingmore preferred and an Mw/Mn of 3 or less and/or a [η] of 1.0 to 3.0 dl/gbeing particularly preferred. A molecular weight distribution (Mw/Mn)exceeding 4 may cause a stickiness in a film or sheet. An intrinsicviscosity [η] less than 0.5 dl/g may also cause a stickiness, while thatexceeding 15.0 dl/g results in a gel or a fish eye in a film or sheet.

An Mw/Mn described above may be understood similarly as in the firstinvention.

In addition to the requirements described above, a fusion endothermiccalorie ΔH determined by DSC of 20 J/g or less allows an inventivepropylenic copolymer [a′] to be more pliable and thus be more preferred.In addition, a propylenic copolymer [a′] in this invention is furtherpreferred when it exhibits no crystallization peak in thecrystallization curve obtained by a differential scanning calorimetry(DSC). One exhibiting any crystallization peak in the crystallizationcurve obtained by a differential scanning calorimetry (DSC) may resultin no film or sheet having an excellent pliability. ΔH, Tm and Tc areobtained as described above.

In addition to the requirements described above, a % boilingdiethylether extract, which is an index for the modulus, of 5% by weightor higher allows a propylenic copolymer [a′] in this invention to befurther preferred. The boiling diethylether extract is determined asdescribed above.

In addition, the tensile elastic modulus is preferably 100 MPa or less,more preferably 70 MPa or less.

In conjunction with a propylenic copolymer [a′] in this invention, anα-olefin having 4 to 20 carbon atoms may for example be ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene andthe like, and, in the invention, these may be employed alone or incombination with each other.

A propylenic copolymer [a′] in this invention is preferably a randomcopolymer. The structural unit derived from propylene exists preferablyat a level of 90% by mole or higher, more preferably 95% by mole orhigher.

[Method for Producing Propylene Homopolymer [a] and Propylenic Copolymer[a′]]

A method for producing a propylene homopolymer [a] and a propyleniccopolymer [a′] in this invention may be a method in which a catalystsystem called a metallocene catalyst is used to homopolymerize propyleneor to copolymerize propylene and ethylene and/or an α-olefin having 4 to20 carbon atoms. In this invention, among metallocene catalysts, onederived from a transition metal compound whose ligand forms acrosslinking structure via a crosslinking group is preferred, and aparticularly preferred method involves a use of a metallocene catalystobtained by combining a transition metal compound whose crosslinkingstructure is formed via 2 crosslinking groups with a promoter wherebyeffecting a homopolymerization of propylene or a copolymerization ofpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms.

Typically, a catalyst consists of the following components.

(A) a transition metal compound(B) a component (B-1) which is a compound capable of forming an ioniccomplex by reacting with a transition metal compound as a component (A)and a component (B-2) which is an aluminoxane.

In addition to a component (A) and a component (B), an organic aluminiumcompound can be used as a component (C).

Components (A), (B) and (C) are similar to those described in the firstinvention, and each of components (B) and (C) may be used alone or incombination of two or more. The amount of each component to be used isalso similar to that employed in the first invention.

In a production method according to the invention, components (A), (B)and (C) may be subjected to a preliminary contact. Such preliminarycontact may be understood as discussed in the first invention.

In the present invention, at least one of the catalyst components may beemployed as being supported on a suitable carrier. A carrier employed inthis invention is similar to that in the first invention. A method forallowing at least one of the catalyst components to be supported on acarrier is also similar to that in the first invention.

In the present invention, a catalyst may be prepared by irradiating adynamic wave upon contact between components (A), (B) and (C). Suchelastic wave is usually a sound wave, preferably an ultrasonic wave.Typically, an ultrasonic wave at a frequency of 1 to 1000 kHz,preferably 10 to 500 kHz may be exemplified.

A catalyst thus obtained may be used in a polymerization after beingisolated as a solid by distilling a solvent off, or alternatively it maybe subjected directly to a polymerization.

In the invention, as is discussed already in the first invention, acatalyst may be produced also by allowing at least one of a component(A) and a component (B) to be supported on a carrier within the systemof polymerization.

The ratio of each component to a carrier is also similar to that in thefirst invention. The polymerization catalyst in this invention thusprepared usually has a mean particle size of 2 to 200 μm, preferably 10to 150 μm, particularly to 100 μm, and a specific surface area usuallyof 20 to 1000 m²/g, preferably 50 to 500 m²/g. In an inventive catalyst,the amount of a transition metal in 100 g of a carrier is usually 0.05to 10 g, preferably 0.1 to 2 g. An amount of a transition metaldeparting from the range described above may result in a reducedactivity.

A propylenic polymer employed in this invention can be produced using apolymerization catalyst described above by homopolymerizing a propyleneor by copolymerizing propylene and ethylene and/or an α-olefin having 4to 20 carbon atoms.

In such procedure, a polymerization method is not particularly limitedand may be a slurry polymerization, a vapor phase polymerization, a bulkpolymerization, a solution polymerization, a suspension polymerizationand the like, and those particularly preferred are a slurrypolymerization and a vapor phase polymerization.

A polymerization condition involves a polymerization temperature usuallyof −100 to 250° C., preferably −50 to 200° C., more preferably 0 to 130°C. The ratio of a catalyst to a reactant, represented as startingmonomer/component (A) (molar ratio), is preferably 1 to 10⁸,particularly 100 to 10⁵. A polymerization time usually of 5 minutes to10 hours, and a reaction pressure preferably of atmospheric pressure to200 kg/cm²G, particularly atmospheric pressure to 100 kg/cm²G areemployed.

The molecular weight of a polymer may be adjusted by appropriatelyselecting the type and the amount of each catalyst component and thepolymerization temperature, or by performing the polymerization in thepresence of hydrogen.

When a polymerization solvent is employed, the types of the solvents maybe similar to those in the first invention. A monomer such as anα-olefin may also be employed as a solvent. Some polymerization methodsneed no use of solvents.

Upon polymerization, a polymerization catalyst described above may beused to perform a preliminary polymerization. Such preliminarypolymerization may be similar to that in the first invention.

As a crystalline propylenic polymer [II] described above, any propylenicpolymer can be employed as far as it exhibits a crystallinity. Thosewhich may be exemplified are a propylene homopolymer, apropylene-ethylene random copolymer, a propylene-ethylene-1-butenerandom copolymer, a propylene-ethylene block copolymer and the like. Themolecular weight of a crystalline propylenic polymer [II] is selectedbased on a desired moldability, and a MI of 2 to 20 g/10 min ispreferred for a T die cast film molding, while one of 1 to 10 g/10 minis preferred for a sheet molding. The selection can be madeappropriately based on the intended use of a film or sheet.Specifically, when an intended use places a significance on the heatresistance and on the heat seal strength, then a highly crystallinepropylene homopolymer is preferred, such as one described inJP-A-8-85711. Thus, one which can be exemplified is a propylenic resinwhich satisfies that:

(1) the % isotactic pentad (P) which is an index for thestereoregularity is 85.0% by mole, the amount of n-heptane-insolublecomponents (H) is 98.0 to 97.0% by weight, and P and H are in therelationship represented by the following formula:

0.750P+27.125<H;

and that (2) the melt index (MI) is 1 to 20 g/10 min and the relaxationtime τ (sec) at the frequency ω0=10° rad/sec based on the frequencydistribution determination at 175° C. and the MI are in the relationshiprepresented by the formula:

τ≦0.65−0.025MI.

More preferable polypropylenic polymer satisfies that: (1′) the %isotactic pentad (P) which is an index for the stereoregularity is 85.0to 92.0% by mole, the amount of n-heptane-insoluble components (H) is86.0 to 97.0% by weight, and P and H are in the relationship representedby the following formula:

0.750P+26.000<H;

and that (2′) the melt index (MI) is 1 to 25 g/10 min and the relaxationtime τ (sec) at the frequency ω0=100 rad/sec based on the frequencydistribution determination at 175° C. and the MI are in the relationshiprepresented by the formula:

τ≦0.63−0.025MI.

The meanings and the determination methods of P, H, MI, ω0 and τdescribed above and the method for producing a propylenic polymer aresimilar to those described in JP-A 8-85711.

For the purpose of improving the low temperature heat seal performanceof a film or sheet, it is preferred that a crystalline propylenicpolymer [II] is also a propylene-ethylene random copolymer or apropylene/ethylene/1-butene random copolymer which has an excellent lowtemperature heat seal performance, such as those described inJP-A-9-208629, JP-A-9-272718, JP-A-10-130336 and the like. Thus, apropylenic copolymer which can be mentioned is a copolymer of propyleneand ethylene which satisfies the following requirements [1] to[5](JP-A-9-208629):

[1] The ethylene unit content (Ω(wt %)) in a copolymer is 3 to wt %;[2] The melt index (MI (g/10 min) of a copolymer is 4 to 12 g/10 min;[3] The boiling diethylether extract: (E (wt %)) and Ω are in therelationship represented the formula (1) or (II):

E≦0.25Ω+1.1 (Ω=3 to 6 wt %)  (I)

E≦2.6 (Ω=6 to 10 wt %)  (II);

[4] The melting point (Tm(° C.)) determined by a differential scanningcalorimeter and x are in the relationship represented by the formula(III) or (IV):

Tm≦140 (Ω=3 to 5 wt %)  (III)

Tm≦165−5Ω (Ω=5 to 10 wt %)  (IV); and,

[5] The % isotactic triad (mm (mol %)) of a PPP chain moiety determinedby ¹³C-NMR is 98.0% by mole or higher.

Also exemplified is a propylenic random copolymer which is a randomcopolymer of propylene and ethylene which satisfies the followingrequirements [1] to [5](JP-A-9-271718):

[1] The ethylene unit content (Ω(wt %)) in a copolymer is 0.2 to 4 wt %;[2] The melt index (MI (g/10 min) of a copolymer is 4 to 12 g/10 min;[3] The boiling diethylether extract (E (wt %)) and Ω are in therelationship represented the formula (1):

E≦0.25Ω+1.1  (1);

[4] The melting point (Tm(° C.)) determined by a differential scanningcalorimeter and Ω are in the relationship represented by the formula(2):

Tm≦165−5Ω  (2); and,

[5] The % isotactic triad (mm (mol %)) of a PPP chain moiety determinedby ¹³C-NMR is 98.0% by mole or higher.

As an ethylene/1-butene/propylene copolymer, one described inJP-A-11-60639 may be exemplified. Thus, a propylenic random copolymerwhich is exemplified is a random copolymer of propylene, ethylene and1-butene which satisfies the following requirements [1] to [6]:

[1] The ethylene unit content in a copolymer (α mol %) and the 1-buteneunit content (β mol %) are in the relationship represented by theformula (1):

4≦α+β≦15  (1);

[2] The melt index of a copolymer (MI (g/10 min) is 1 to 12 g/10 min;[3] The boiling diethylether extract (E) and (α+β) are in therelationship represented by the formula (2) when (α+β)≦12 and by theformula (3) when (α+β)≧12:

E≦0.2(α+β)+0.6  (2)

E≦3.0  (3)

[4] The melting point (Tm(° C.)) determined by a differential scanningcalorimeter and (α+β) are in the relationship represented by the formula(4):

Tm≦164−3.6(α+β)  (4)

[5] The stereoregularity index P (mol %) determined by ¹³C-NMR is 98% bymole or higher; and,[6] The ratio (Mw/Mn) of the weight mean molecular weight (Mw) to thenumber mean molecular weight (Mn) determined by a gel permeationchromatography (GPC) is 6 or less (JP-A-11-60639).

The meaning and the determination method of each parameter are asdescribed in the respective publication.

When as a crystalline propylenic polymer [II] in this invention oneexhibiting no crystallinity is employed, the heat resistance of a filmor sheet may be reduced.

In this invention, a propylenic polymer [I] and a crystalline propylenicpolymer [II] may be dry-blended using a Henschel mixer and the like, or,alternatively, they may be kneaded using a single- or twin-screwextruder, Banbury mixer and the like. A component [I] is incorporated inan amount of 1 to 99% by weight, preferably 10 to 90% by weight,particularly 20 to 80% by weight. When an amount of a component [I] lessthan 1% by weight or less, the pliability may be reduced.

To a propylenic resin composition in this invention, various additivesmay be added if desired. Such additives may be antioxidant, neutralizingagent, slipperiness-imparting agent, anti-blocking agent, anti-frostingagent, antistatic agent and the like. Each of such additives may beemployed alone or as a combination of two or more. For example, aphosphorus-based antioxidant, a phenol-based antioxidant and asulfur-based antioxidant may be exemplified as an antioxidant.

A phosphorus-based antioxidant may for example betrisnonylpheylphosphite, tris(2,4-di-t-butylphenyl)phosphite,distearylpentaerythritol diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol phosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol phosphite,2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite,tetrakis(2,4-di-t-butylphenyl)-4,4-bophenylene-di-phosphite, ADECASTAB1178 (ASAHI DENKA), SMILIZER TNP (SUMITOMO KAGAKU), JP-135 (JOHOKUKAGAKU), ADECASTAB 2112 (ASAHI DENKA), JPP-2000 (JOHOKU KAGAKU), Weston618 (GE), ADECASTAB PEP-24G (ASAHI DENKA), ADECASTAB PEP-36 (ASAHIDENKA), ADECASTAB HP-10 (ASAHI DENKA), SandstabP-EPQ (SANDZ), phosphite168 (Ciba-geigy) and the like.

A phenol-based antioxidant may for example be2,6-di-t-butyl-4-methylphenol,n-octadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl]methane,tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,4,4′-butylidenebis-(3-methyl-6-t-butylphenol),triethyleneglycol-bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate],3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5undecane,SMILIZER BHT (SUMITOMO KAGAKU), YOSHINOX BHT (YOSHITOMI PHARMACEUTICALCO., LTD.), ANTAGE BHT (KAWAGUCHI KAGAKU), IRGANOX 1076 (Ciba-geigy),IRGANOX 1010 (Ciba-geigy), ADECASTAB AO-60 (ASAHI DENKA), SMILIZERBP-101 (SUMITOMO KAGAKU), TOMINOX TT (YOSHITOMI PHARMACEUTICAL CO.,LTD.), TTHP (TORAY), IRGANOX 3114 (Ciba-geigy), ADECASTAB AO-40 (ASAHIDENKA), SMILIZER BBM-S (SUMITOMO KAGAKU), YOSHINOX BB (YOSHITOMIPHARMACEUTICAL CO., LTD.), ANTAGE W-300 (KAWAGUCHI KAGAKU), IRGANOX 245(Ciba-geigy), ADECASTAB AO-70 (ASAHI DENKA), TOMINOX 917 (YOSHITOMI),ADECASTAB AO-80 (ASAHI DENKA), SMILIZER GA-80 (SUMITOMO KAGAKU) and thelike.

A sulfur-based antioxidant may for example bedilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate,distearyl-3,3′-thiodipropionate,pentaerythritoltetrakis(3-laurylthiopropionate), SMILIZER TPL (SUMITOMOKAGAKU), YOSHINOX DLTP (YOSHITOMI), ANTIOX L (NIPPON YUSHI), SMILIZERTPM (SUMITOMO KAGAKU), YOSHINOX DMTP (YOSHITOMI), ANTIOX M (NIPPONYUSHI), SMILIZER TPS (SUMITOMO KAGAKU), YOSHINOX DSTP (YOSHITOMI),ANTIOX S (NIPPON YUSHI), ADECASTAB AO-412S (ASAHI DENKA), SEENOX 412S(CYPLO KASEI), SMILIZER TDP (SUMITOMO KAGAKU) and the like.

As an antioxidant for a film or sheet, IRGANOX 1010: general name:pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],IRGAPHOS 168: general name: tris(2,4-di-t-butylphenyl)phosphite, IRGANOX1076: general name:octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, IRGANOX 1330:general name:1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,IRGANOX 3114: general name:tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, P-EPQ: general name:tetrakis(2,4-di-t-butylphenyl) 4,4′-biphenylene-di-phosphite areparticularly preferred.

When an antioxidant is employed in this invention, it is added in anamount of 0.001 to 1 parts by weight to 100 parts by weight of apropylenic resin composition described above. As a result, a preferableeffect such as prevention of yellowing is achieved.

Typically, an antioxidant listed above may be incorporated as follows.

Case 1

IRGANOX 1010 1000 ppm PEP-Q 1000 ppm

Case 2

IRGANOX 1076 1200 ppm  PEP-Q 600 ppm IRGAPHOS 168 800 ppm

Case 3

IRGANOX 1010 400 to 1000 ppm IRGAPHOS 168 750 to 1500 ppm

A particularly preferred neutralizing agent for a film and sheet may forexample be calcium stearate, zinc stearate, magnesium stearate,HYDROTALSITE (DHT-4A): empirical formula: Mg4.5Al2(OH)13CO₃3.5H₂O andthe like.

A particularly preferred antiblocking agent for a film and sheet may forexample be PSYLICIA:a synthesized silica-based material manufactured byFUJI SILICIA, MIZUKASIL:a synthesized silica-based material manufacturedby MIZUSAWA KAGAKU KOGYO and the like.

A particularly preferred slipperiness-imparting agent for a film andsheet may for example be erucic acid amide, oleic acid amide, stearicacid amide, behenic acid amide, ethylene bisstearic acid amide, ethylenebis oleic acid amide, stearylerucaamide and oleylpalmitoamide.

When a nucleating agent is used in this invention, the amount of anucleating agent to be added is 10 ppm or higher, preferably 10 to 10000ppm, more preferably 10 to 5000 ppm, particularly 10 to 2500 ppm, basedon a propylenic resin composition. An amount less than 10 ppm providesno improvement in the heat seal performance, while an amount exceeding10000 ppm fails to exhibit corresponding increase in the effect and mayrather lead to a poor appearance. A nucleating agent may be understoodas is discussed in the first invention.

[VI] Sixth Invention

The sixth invention is detailed below.

[1] A resin composition in this invention is a polypropylenic resincomposition comprising (A) 99 to 50% by weight of a propylenehomopolymer having the following characteristics(a1) to (a4):(a1) the intrinsic viscosity [η] is 0.5 to 5.0 dl/g;(a2) the molecular weight distribution (Mw/Mn) is 3.5 or less;(a3) the isotactic pentad fraction (mmmm (in percentage terms by mole))is 40 to 99% by mole; and,(a4) the isotactic pentad fraction (mmmm (in percentage terms by mole))and the melting point (Tm(° C.)) are in the relationship represented bythe following formula (1):

Tm≦[mmmm]+65  (I);

and,(B) 1 to 50% by weight of a propylene homopolymer capable of forming aneutectic with a component (A) under a rapid cooling condition upon filmformation.

Since a propylene homopolymer as a component (A) which has a narrowmolecular weight distribution is analogous in its nature to a singlecomponent material, it has a smaller amount of a polymer having adifferent stereoregularity or a low molecular weight polymer whichserves as a crystallization nucleus at the initial stage of thecrystallization, resulting in a difficulty in the crystallization, whichleads to an increase in the supercooling degree (difference intemperature between the melting point and the crystallizationtemperature) which is indicative of a crystallization profile.

In this invention, by means of an eutectic formation of a propylenehomopolymer as a component (A) having a narrow molecular weightdistribution with other propylene homopolymer as a component (B) under arapid cooling condition upon film formation, an improvement in themoldability, which is difficult to be achieved with a singlepolypropylene, can be achieved, and a cast film whose rigidity and sealtemperature are well-balanced can be obtained.

In general, a determination in an almost equilibrated process of acrystal growth such as in DSC may involve a difficulty in an eutecticformation and may exhibit a supercooling degree which is observed to bereduced only slightly.

On the contrary, a heat molding of a film or sheet employs a rapidcooling for setting (non-equilibrated process of a crystal growth) whichallows an eutectic to be formed readily, and this eutectic formationcontributes to the improvement in the physical characteristics and inthe moldability.

Thus, a component (B) in this invention may be one capable of forming aneutectic with a component (A) under a rapid cooling condition upon filmformation (on the basis of the resin temperature at the exit of a die of191° C., the chill roll temperature of 30° C., the film thickness of 25g, the haul-off speed of 6 mm/min).

A eutectic formation of a polymer in this invention is defined so when asingle peak top is observed in a fusion endothermic curve obtained byraising the temperature immediately after conditioning a film, which hasjust been molded, as described later using a differential scanningcalorimetry (DSC method). This eutectic formation of a polymer isunderstood to be a process in which one polymer undergoes an initialcrystal formation utilizing the other polymer as a crystallizationnucleus and a subsequent crystal growth takes place.

While a propylene homopolymer as a component (A) is a polypropylenewhich is polymerized with a homogeneous catalyst such as a metallocenecatalyst, any catalyst having a performance close to that of ahomogeneous system may be employed even if it is a supported catalystsuch as a Ziegler-Natta catalyst. Thus, without limitation to a catalystemployed in a polymerization, a propylene homopolymer whose intrinsicviscosity [η] is 0.5 to 5.0 dl/g, molecular weight distribution (Mw/Mn)is 3.5 or less, % isotactic pentad (mmmm % by mole) is 40 to 99% bymole, preferably 80 to 99% by mole, and % isotactic pentad (mmmm % bymole) and melting point (Tm(° C.)) are in the relationship representedby the following formula (1):

Tm≦[mmmm]+65  (I);

is acceptable.

An intrinsic viscosity [η] less than 0.5 dl/g results in a shortcomingin the mechanical strength of a film such as tensile strength andrigidity, while one higher than 5.0 dl/g results in a difficulty inextrusion moldings such as cast molding, and a molecular weightdistribution (Mw/Mn) exceeding 3.5 results in an impairment in thebalance between the rigidity and the heat seal performance of a film ora reduction in the anti-blocking performance. A % isotactic pentad (mmmm% by mole) less than 40% by mole results in a lower rigidity of a film,while one exceeding 90% by mole results in a disadvantageously poorimpact resistance of a film.

The formula (I) representing the relationship between the isotacticpentad fraction (mmmm (in percentage terms by mole)) and the meltingpoint (Tm ° C.) is defined for the purpose of excluding a polypropylenewhose molecular weight distribution (Mw/Mn) of 3.5 or less obtained bymeans of a use of a peroxide for decomposing a polypropylene having abroad molecular weight distribution obtained by a conventional catalyst.While a propylene homopolymer as a component (A) in this invention has astereoregularity [mmmm] and a molecular weight which are close to thoseof a single component material, one excluded as described above is amixture of various components having different levels of thestereoregularity [mmmm] and tends to exhibits a higher melting point (Tm° C.) inherent to a resin composition reflecting the presence of acomponent having a high stereoregularity [mmmm], because of which it isexcluded by Formula (I). One departing from the relationship representedby Formula (I) provides a film having a poor balance between therigidity and the heat seal temperature.

A propylene homopolymer as a component (B) may be one capable of formingan eutectic with a propylene homopolymer as a component (A).

In general, one having a stereoregularity and a molecular weight whichare different from those of a propylene homopolymer as a component (A)can induce a crystallization nucleus and form an eutectic. Accordingly,a propylene homopolymer having a molecular weight which is smaller thanthat of a component (A) may be exemplified.

An inventive resin composition is a polypropylenic resin compositioncomprising 99 to 50% by weight, more preferably 99 to 80% by weight of acomponent (A), and 1 to 50% by weight, more preferably 1 to 20% byweight of a component (B).

An amount of a component (B) less than 1% by weight results indeteriorated heat seal performance and moldability, while that exceeding50% by weight results in an impairment in the balance between the heatseal performance and the rigidity of a film.

A film produced by a cast molding using a resin composition whosecrystallization profile is improved has a higher ability of improvingthe physical characteristics and a higher ability of improving themoldability, and a resultant cast-molded film has a tensile modulus inthe direction of MD (TM(MPa) and a heat seal temperature (HST(° C.)) areexpected to be in the relationship represented by the following Formula(II):

TM≧22×HST−1850  (II);

more preferably by the following Formula (II′):

TM≧22×HST−1800  (II′).

Formula [II] reflects the fact that the effect according to theinvention serves to allow the heat seal temperature (HST(° C.)) to befurther lowered (whereby achieving an intended seal pealing strength ata lower temperature) and also serves to allow the film tensile modulus(rigidity) to be improved.

[2] Also this invention is a polypropylenic resin composition which isincluded in a resin composition [1] described above and in which thecrystallization temperature (TcB ° C.) of a component (B) determined bya differential scanning calorimeter is higher by 0 to 40° C. than that(TcA ° C.) of a component (A).

Thus, a component (B) capable of forming an eutectic with a component(A) exhibits a higher physical characteristics-improving effect when thedifference in the crystallization temperature between the two componentsbecomes greater, but a difference exceeding 40° C. results in adifficulty in forming an eutectic, which may lead to no physicalcharacteristics-improving effect according to the invention to beexpected. More preferably, TcB is higher by to 40° C. than TcA.

[3] Furthermore, this invention is a polypropylenic resin compositioncomprising (A′) 99 to 50% by weight of a propylenic polymer obtained bya polymerization using a metallocene catalyst which is a propylenehomopolymer and has an isotactic pentad fraction (mmmm) of 80 to 99%, anintrinsic viscosity [η] of 1.0 to 2.0 dl/g and a molecular weightdistribution (Mw/Mn ratio) of 3.5 or less, and, (B′) 1 to 50% by weightof a propylenic polymer obtained by a polymerization using a metallocenecatalyst which is a propylene homopolymer and has an intrinsic viscosity[η] of 0.01 to 1.0 dl/g and a molecular weight distribution (Mw/Mnratio) of 3.5 or less.

(1) Component (A′)

A component (A′) may be a propylenic polymer which is a propylenehomopolymer polymerized using a metallocene catalyst and also may be apropylenic polymer which has been subjected to a preliminarypolymerization with a small amount (0.5% by mole or less) of ethylene oran α-olefin having 4 to 20 carbon atoms, wherein the % isotactic pentad(% mmmm), which is indicative of the stereoregularity of thepolypropylene, is 80 to 99%, more preferably 85 to 97%, the intrinsicviscosity [η] is 1.0 to 2.0 dl/g, more preferably 1.5 to 1.8 dl/g, andthe molecular weight distribution (Mw/Mn ratio) is 3.5 or less, morepreferably 3.0 or less.

A % isotactic pentad referred herein means the proportion (%) of thepropylene structure units each having a meso-structure (mmmm structurein which 5 methyl groups are aligned in the same direction) in 5propylene structure unit based on the assignment of the peaks in a¹³C-NMR spectrum described by Chen H. N., Ewen J. A., Macromol. cem.,1989, 190, 1350. Such proportion is abbreviated as a % meso-pentad.

A % isotactic pentad described, above which is less than 80% may resultin an insufficient film rigidity, while that exceeding 99% may result adisadvantageous reduction in the impact resistance of a film.

An intrinsic viscosity [η] is usually preferable to be within the rangefrom 1.0 to 2.0 dl/g for the purpose of a better film moldability, andone less than 1.0 dl/g results in insufficient tensile strength andrigidity of a film, while one exceeding 2.0 dl/g may cause a reducedflowability which may lead to a poor moldability.

Furthermore, a molecular weight distribution (Mw/Mn ratio) exceeding 3.5may cause an impairment in the balance between the rigidity and the heatseal performance of a film or a reduction in the anti-blockingperformance.

A propylenic polymer as a component (A′) employed in this invention canbe produced by a polymerization in the presence of a metallocenecatalyst comprising a cyclopentadienyl group-carrying compound of atransition metal of Group IV in the periodic table and amethylaluminoxane or a compound capable of forming an ionic complex byreacting with a compound of a transition metal of Group IV in theperiodic table and an organic aluminium compound.

A main catalyst, which is a cyclopentadienyl group-carrying compound ofa transition metal of Group IV in the periodic table may be a compoundof zirconium, titanium and hafnium having as a ligand a multi dentatecoordination compound in which at least two groups selected from thegroup consisting of cycloalkadienyl groups or their substitutedderivatives, typically, an indenyl group, a substituted indenyl groupand its partially hydrogenated derivative are bound via a lower alkylenegroup or silylene group. Thus, a transition metal compound may beethylene-bis-(indenyl)zirconium dichloride described by H. H.Brintzinger et al. In J. Organometal. Chem., 288, 63 (1985), orethylene-bis-(indenyl)hafnium dichloride described in J. Am. Chem. Soc.,109, 6544 (1987), and a stereorigid chiral compound of zirconium andhafnium compounds such asdimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride,dimethylsilylbis(2,4,5-trimethylcyclopentadienyl)zirconium dichlorideand hafnium dichlorides of the similar complexes, as described by H.Yamazaki et al. in Chemistry Letters, 1853 (1989).

Those exemplified typically are ethylenebis(indenyl)zirconiumdichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride,ethylenebis(5-methyl-1-indenyl)zirconium dichloride,ethylenebis(6-methyl-1-indenyl)zirconium dichloride,ethylenebis(7-methyl-1-indenyl)zirconium dichloride,ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride,ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride,ethylenebis(indenyl)hafnium dichloride,ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride,ethylenebis(4-methyl-1-indenyl)hafnium dichloride,ethylenebis(5-methyl-1-indenyl)hafnium dichloride,ethylenebis(6-methyl-1-indenyl)hafnium dichloride,ethylenebis(7-methyl-1-indenyl)hafnium dichloride,ethylenebis(2,3-dimethyl-1-indenyl)hafnium dichloride,ethylenebis(4,7-dimethyl-1-indenyl)hafnium dichloride,dimethylsilylenebis(indenyl)zirconium dichloride,dimethylsilylenebis(indenyl)hafnium dichloride,dimethylsilylenebis(4-methylindenyl)zirconium dichloride,dimethylsilylenebis(indenyl)hafnium dichloride,dimethylsilylenebis(2,4,5-trimethylcyclopentadienyl)zirconiumdichloride, dimethylsilylenebis(2,4,5-trimethyl cyclopentadienyl)hafniumdichloride, dimethylsilylenebis(2,4-dimethylcyclopentadienyl)zirconiumdichloride, dimethylsilylenebis(2,4-dimethylcyclopentadienyl)hafniumdichloride, dimethylsilylenebis(3-methylcyclopentadienyl)zirconiumdichloride, dimethylsilylenebis(3-methylcyclopentadienyl)hafniumdichloride, dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconiumdichloride, dimethylsilylenebis(benzoindenyl)zirconium dichloride andthe like.

Those which may also be exemplified are(dimethylsilylene)(dimethylsilylene)-bis(indenyl)zirconium dichloride,(ethylene)(ethylene)-bis(indenyl)zirconium dichloride,(ethylene)(ethylene)-bis(3-methylindenyl)zirconium dichloride,(ethylene)(ethylene)-bis(4,7-dimethylindenyl)zirconium dichloride andthe like, as well as those obtained by replacing zirconium in thesecompounds with hafnium or titanium.

As a compound capable of forming an ionic complex by reacting with acompound of a transition metal of Group IV in the periodic table whichis a promoter, those employed preferably may for example be atetra(pentafluorophenyl)borate anion-containing compound such astriphenylcarbynium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate and the like, as well as atetra(pentafluorophenyl)aluminate anion-containing compound such astriphenylcarbynium tetrakis(pentafluorophenyl)aluminate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate.

An organic aluminium compound is one having at least one Al—C binding inits molecule. Typically, such organic aluminium compound may for examplebe a trialkylaluminium such as triethylaluminium, triisobutylaluminium,trihexylaluminum and the like, a dialkylaluminum halide such asdiethylaluminium halide, diisobutylaluminium halide and the like, amixture of a trialkylaluminium and dialkylaluminum halide, and analkylalumoxane such as tetraethyldialumoxane, tetrabutylalumoxane andthe like.

Among these organic aluminum compounds, those employed preferably are atrialkylaluminium, a mixture of a trialkylaluminium and adialkylaluminum halide and an alkylalumoxane, with triethylaluminium,triisobutylaluminium, a mixture of triethylaluminium anddiethylaluminium chloride and tetraethyldialumoxane being particularlypreferred. As an organic aluminium, those employed preferably aretriethylaluminium, triisobutylaluminium and the like.

These metallocene-based catalyst and/or promoter may be employed also asbeing supported on a carrier, and such carrier may for example be anorganic compound such as polystyrene as well as an inorganic oxide suchas silica, alumina and the like.

A polymerization method may be a bulk polymerization, a solutionpolymerization, a vapor phase polymerization, a suspensionpolymerization and the like, and may be performed as a batch process ora continuous process.

It is also possible that a small amount of α-olefin such as ethylene,propylene, 1-butene, 4-methyl-1-pentene and the like is used to performa preliminary polymerization.

A polymerization is conducted at a temperature usually of −50 to 250°C., preferably 0 to 150° C., for a period usually of 1 to 10 hour(s), ata pressure usually of atmospheric pressure to 300 kg/cm²-G.

(2) Component (B′)

A component (B′) may be a propylene homopolymer polymerized using ametallocene catalyst and also may be a propylenic polymer which has beensubjected to a preliminary polymerization with a small amount (0.5% bymole or less) of ethylene or an α-olefin having 4 to 20 carbon atoms,wherein the intrinsic viscosity [η] is 0.01 to 1.0 dl/g, more preferably0.1 to 0.8 dl/g and the molecular weight distribution (Mw/Mn ratio) is3.5 or less, more preferably 3.0 or less.

An intrinsic viscosity [η] less than 0.01 dl/g may cause a stickiness ina film, while one exceeding 1.0 dl/g fails to improve the balancebetween the rigidity and the heat seal performance of a film.

On the other hand, a molecular weight distribution (Mw/Mn ratio)exceeding 3.5 results in an impairment in the balance between therigidity and the heat seal performance of a film or a reduction in theanti-blocking performance.

While the % isotactic pentad (% mmmm) of a component (B′) is notparticularly limited, it is preferably 80 to 99% for the purpose of abetter film rigidity. In addition, it is preferred that thecrystallization temperature Tc of a component (B′) is higher than thatof a component (A′).

A polymerization of a component (B′) may basically use ametallocene-based catalyst and the promoter similar to those employedfor the propylenic polymer as a compound (A′) described above, and theproduction may be performed also by the similar polymerization method.

(3) Incorporation

An inventive propylenic polymer composition employs the incorporationratio (ratio in % by weight) of a component (A′) and a component (B′)which is 99 to 50:1 to 50. More preferably, the ratio is 99 to 75:1 to25, particularly 99 to 90:1 to 10.

A content of a component (B) less than 1% may results in a deterioratedheat seal performance, while that exceeding 50% by weight results in animpairment in the balance between the rigidity and the heat sealperformance of a film.

When combining a component (A) with a component (B) or a component (A′)with a component (B′) according to the invention, various additives suchas nucleating agent, heat stabilizing agent, antioxidant, weatheringagent, neutralizing agent, slipperiness-imparting agent, anti-blockingagent, glidant, dye, pigment, filler, anti-frosting agent, antistaticagent and the like may be incorporated as desired.

A propylenic polymer composition can be obtained by mixing respectivecomponents described above using Henschel mixer, V blender, ribbonblender, tumbler blender and the like, followed by kneading the mixtureusing a kneading device such as single- or multi-screw extruder,kneader, Banbury mixer and the like.

[4] An inventive propylenic polymer composition can be applied also toan injection molding, a blow molding, an extrusion molding and the like,among which the application to a cast-molded or inflation-molded film isespecially preferred. The thickness of a film may vary depending on theuses, and is usually about 5 to 500 μm. A film described above can notonly be used as a single-layered film but can also be fabricated into amulti-layered film by means of a co-extrusion film forming process, andis used preferably also as an oriented film.

[VII] Seventh Invention

The seventh invention is detailed below.

[1] A resin composition in this invention is a propylenic resincomprising 99 to 50% by weight of a propylene-α-olefin copolymer (A′)having the following characteristics (a1) to (a5):(a1) the intrinsic viscosity [η] is 0.5 to 5 dl/g, preferably 0.7 to 2.5dl/g, more preferably 1.0 to 2.0 dl/g;(a2) the molecular weight distribution (Mw/Mn) is 3.5 or less,preferably 3.0 or less, more preferably 2.5 or less;(a3) the stereoregularity index (P) is 5 to 99% by mole, preferably 55to 95% by mole, more preferably 55 to 90% by mole;(a4) it is a propylenic random copolymer produced by copolymerizingpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms,in which the ethylene and/or an α-olefin having 4 to 20 carbon atoms iscontained in an amount of 1 to 30% by mole; and,(a5) the amount of the components which are dissolved out at 0° C. orlower in a temperature-raising fractional chromatography (TREF) is 10%by weight or less, preferably 8% by weight or less, more preferably 5%by weight or less; and,1 to 50% by weight or a propylenic polymer (B′) capable of forming aneutectic with a component (A′) under a rapid cooling condition upon filmformation.

Since a propylene-α-olefin copolymer as a component (A′) which has anarrow molecular weight distribution is analogous in its nature to asingle component material (a copolymer whose molecular weight andcomonomer ratio are uniform), it has a smaller amount of a polymerhaving a different stereoregularity or a low molecular weight polymerwhich serves as a crystallization nucleus at the initial stage of thecrystallization, resulting in a difficulty in the crystallization, whichleads to an increase in the supercooling degree (difference intemperature between the melting point and the crystallizationtemperature) which is indicative of a crystallization profile.

In this invention, by means of an eutectic formation of apropylene-α-olefin copolymer as a component (A′) having a narrowmolecular weight distribution with other propylene polymer as acomponent (B′) under a rapid cooling condition upon film formation, animprovement in the moldability, which is difficult to be achieved with asingle propylene-α-olefin copolymer, can be achieved, and a cast filmwhose rigidity and seal temperature are well-balanced can be obtained.

In general, a determination of a crystallization temperature in analmost equilibrated process of a crystal growth such as in adifferential scanning calorimetry (DSC) may involve a difficulty in aneutectic formation and may exhibit a supercooling degree which isobserved to be reduced only slightly.

On the contrary, a heat molding of a film or sheet employs a rapidcooling for setting (non-equilibrated process of a crystal growth) whichallows an eutectic to be formed readily, and this eutectic formationcontributes to the improvement in the physical characteristics and inthe moldability.

Thus, a component (B′) in this invention may be one capable of formingan eutectic with a component (A′) under a rapid cooling condition uponfilm formation (on the basis of the resin temperature at the exit of adie of 191° C., the chill roll temperature of 30° C., the film thicknessof 25μ, the haul-off speed of 6 mm/min).

A eutectic formation of a polymer in this invention is defined so whenthe peak top observed in a fusion endothermic curve obtained bysubjecting a film, which has just been molded, to a differentialscanning calorimetry (DSC) is single and the crystallization temperatureof this film is higher than that of a component (A′) and lower than thatof a component (B′). This eutectic formation of a polymer is understoodto be a process in which one polymer undergoes an initial crystalformation utilizing the other polymer as a crystallization nucleus and asubsequent crystal growth takes place.

While a propylene-α-olefin copolymer as a component (A′) employed inthis invention is a polypropylene which is polymerized with ahomogeneous catalyst such as a metallocene catalyst using a knownproduction method such as vapor phase and solution polymerizations, anycatalyst having a performance close to that of a homogeneous system,i.e., ability of providing a polymer having the parameters shown in thesections (a1) to (a5) described above, may be employed even if it is asupported catalyst such as a Ziegler-Natta catalyst. Typical catalystsand production examples are discussed later in above [4][Examples ofproduction of resins and films], and the methods for determining theparameters shown in the sections (a1) to (a5) described above arediscussed later in the part of [Examples].

An intrinsic viscosity [η] less than 0.5 dl/g results in a shortcomingin the mechanical strength of a film such as tensile strength andrigidity, while one higher than 5.0 dl/g results in a difficulty inextrusion moldings such as cast molding, and a molecular weightdistribution (Mw/Mn) exceeding 3.5 results in an impairment in thebalance between the rigidity and the heat seal performance of a film ora reduction in the anti-blocking performance. A % isotactic pentad (mmmm% by mole), which is a stereoregularity index (P), less than 50% by moleresults in a lower rigidity of a film, while one exceeding 90% by moleresults in a disadvantageously poor impact resistance of a film.

This invention is also a propylenic random copolymer produced bycopolymerizing propylene and ethylene and/or an α-olefin having 4 to 20carbon atoms, and an α-olefin whose number of the constituent carbonatoms exceeds 20 exhibits a low activity which leads to a residual oil,and the amount of ethylene and/or an α-olefin having 4 to 20 carbonatoms less than 0.1% by mole gives a less improving effect, while thatexceeding 30% by mole in results in a difficulty in the molding.

An amount of the components which are dissolved out at 0° C. or lower ina temperature-raising fractional chromatography (TREF) exceeding 10% byweight results in a disadvantageously apparent stickiness in a film.Thus, a polypropylene having a higher level of a copolymer of a lowα-olefin content which may serve as a stickiness-impairing component ina film is intended to be excluded even if its molecular weight isadjusted to 3.5 or less by subjecting a propylene-α-olefin copolymerwhich is obtained using a conventional catalyst and has a broadmolecular weight distribution and a broad range of the comonomer ratioin the copolymer (a mixture of copolymers having different comonomerratio) to a decomposition using a peroxide.

A propylene homopolymer as a component (B′) may be one capable offorming an eutectic with a propylene homopolymer as a component (A′).

In general, one having a stereoregularity and a molecular weight whichare different from those of a propylene-α-olefin copolymer as acomponent (A′) can induce a crystallization nucleus and form aneutectic. Accordingly, a propylene homopolymer, a propylene-α-olefincopolymer, which has a molecular weight which is smaller than that of acomponent (A′) may be exemplified. Among these, a propylenic polymerwhose stereoregularity index (P) is preferably 85% by mole, morepreferably 90% by mole, particularly 95 5 by mole is desirable.

Such component (B′) may also be produced by a known method similarly toa component (A′) discussed above.

An inventive resin composition is a polypropylenic resin compositioncomprising 99 to 50% by weight, more preferably 99 to 80% by weight of acomponent (A′), and 1 to 50% by weight, more preferably 1 to 20% byweight of a component (B′).

An amount of a component (B′) less than 1% by weight results indeteriorated heat seal performance and moldability, while that exceeding50% by weight results in an impairment in the balance between the heatseal performance and the rigidity of a film.

A film produced by a cast molding using a resin composition whosecrystallization profile is improved has a higher ability of improvingthe physical characteristics and a higher ability of improving themoldability, and a resultant cast-molded film has a tensile modulus inthe direction of MD (TM(MPa) and a heat seal temperature (HST(° C.)) areexpected to be in the relationship represented by the following Formula(II):

TM≧22×HST−1850  (II);

more preferably by the following Formula (II′):

TM≧22×HST−1800  (II′).

Formula [II] reflects the fact that the effect according to theinvention serves to allow the heat seal temperature (HST(° C.)) to befurther lowered (whereby achieving an intended seal pealing strength ata lower temperature) and also serves to allow the film tensile modulus(rigidity) to be improved.

[2] Also this invention is a polypropylenic resin composition which isincluded in the invention [1] described above and in which thecrystallization temperature (TcB ° C.) of a component (B) determined bya differential scanning calorimeter is higher by 0 to 40° C. than that(TcA ° C.) of a component (A).

Thus, a component (B) capable of forming an eutectic with a component(A) exhibits a higher physical characteristics-improving effect when thedifference in the crystallization temperature between the two componentsbecomes greater, but a difference exceeding 40° C. results in adifficulty in forming an: eutectic, which may lead to no physicalcharacteristics-improving effect according to the invention to beexpected. More preferably, TcB is higher by to 40° C. than TcA.

[3] Furthermore, this invention is a polypropylenic resin comprising acopolymer (A) of propylene and an α-olefin having or more carbon atomsand a propylenic polymer (B) having a crystallization temperaturedetermined by a differential scanning calorimetry which is higher thanthat of the component (A), wherein (A) is present in an amount of 55 to99 parts by weight and (B) in an amount of 45 to 1 parts by weight.

In this invention, a copolymer (A) should be a copolymer of propyleneand an α-olefin having 5 or more carbon atoms. A propylene homopolymeris not preferred since it gives an insufficient low temperature heatseal performance. An α-olefin having 5 or more carbon atoms is notparticularly limited, and may typically be 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 11-octadecene and the like. Among these α-olefins, atleast one of 1-octene, 1-dodecene and 1-decene is employed to perform apreferable copolymerization with propylene. When an ethylene unit or a1-butene unit is employed as an α-olefin, the ability of lowering themelting point of a polypropylene becomes lower than when an α-olefinhaving 5 or more carbon atom is employed, resulting in an insufficientability of improving the low temperature heat seal characteristics.

Also in this invention, it is preferable that a copolymer (A) satisfiesthe following requirements (A-1) or (A-2): (A-1) when the main elutionpeak temperature of a temperature-raising fractional chromatogram is Tp,the amount (W(A)p) of the components dissolved out within thetemperature range from (Tp−5) ° C. to (Tp+5) ° C. is 70% by weight ormore; and,

(A-2) the amount (W(A)0) of the components dissolved out at 0° C. orlower in a temperature-raising fractional chromatography is 3% by weightor less.

In this context, W(A)p is more preferably 75% by weight or higher,particularly 80% by weight or higher. AW(A)p less than 70% by weightmeans a broad composition distribution, which allows the peaks otherthan the main elution peak to appear on a TREF curve or which allows themain elution peak to exhibit a long tailing in the direction of the highor low temperature. Such case is excluded from the preferable rangebecause of the reasons described below. Thus, when the main elution peakexhibits a tailing in the direction of the high temperature or when asecondary peak is observed at a higher temperature than the temperatureat which the main elution peak is observed, the heat seal performancetends to be insufficient. On the contrary, when the main elution peakexhibits a tailing in the direction of the low temperature or when asecondary peak is observed at a lower temperature than the temperatureat which the main elution peak is observed, a resultant film, fiber,sheet or molded article exhibits a disadvantageous stickiness. W(A)0 ispreferably 2% by weight or less. More preferably, it is 1.5% by weightor less. A value of W(A)0 exceeding 3% by weight results in a resultantfilm, fiber, sheet or molded article which may exhibit a disadvantageousstickiness.

Also in this invention, it is preferable that a copolymer (A) satisfiesat least one of the following requirements (A-3), (A-4) or (A-5):

(A-3) a copolymer (A) contains an α-olefin unit having 5 or more carbonatoms in an amount (a % by mole) of 0.1 to 12% by mole;(A-4) the stereoregularity index (P) of a copolymer (A) is 85% by moleor higher; and,(A-5) a copolymer (A) has an intrinsic viscosity [1] determined in adecalin at 135° C. ranges from 0.5 to 3.0 dl/g.

In this invention, it is preferable that a copolymer (A) contains anα-olefin unit having 5 or more carbon atoms in an amount (α % by mole)of 0.1 to 12% by mole. More preferably the amount is 0.2% by mole orhigher and not more than 11% by mole. Particularly, the amount is 0.3%by mole or higher and not more than 10% by mole. An amount less than0.1% by mole may result in an insufficient ability of improving the heatseal performance. On the other hand, an amount exceeding 12% by molecauses an reduction in the copolymer crystallinity which may lead to adisadvantageously poor rigidity. The stereoregurality index (P) is morepreferably 90% by mole or higher. Particularly, it is 95% by mole orhigher. A stereoregularity index (P) less than 85% by mole causes anreduction in the copolymer crystallinity which may lead to a poorrigidity. A stereoregularity index (P) is a % isotactic moiety in atriad unit determined by ¹³C-NMR, and the method for determination isdetailed in Examples. The value of [η] is preferred to be within therange from 0.5 to 3.0 dl/g, a value departing from which may cause apoor molding performance.

In this invention, the melting point (Tma ° C.) of a copolymer (A)determined in a differential scanning calorimetry is in the relationshiprepresented the following formula:

Tma≦140° C. and Tma≦160−7α  (2);

more preferably by the following formula:

Tma≦130° C. and Tma≦155−7α  (3);

further preferably by the following formula:

Tma≦120° C. and Tma≦150−7α  (4);

particularly by the following formula:

Tma≦115° C. and Tma≦145−7α  (5).

A value of Tma departing from the range specified above may result in aninsufficient low temperature heat seal performance.

In this invention, a propylenic polymer (B) should has a crystallizationtemperature determined by a differential scanning calorimeter which ishigher than that of a copolymer (A). The composition and the structureof a propylenic polymer (B) is not particularly limited, and one whichmay be employed is a polypropylene homopolymer or a copolymer ofpropylene with other α-olefin. As a polypropylene homopolymer, anisotactic polypropylene having a higher stereoregularity is preferred.Typically, one employed preferably has a % isotactic pentad, which is anindex of the stereoregularity, of 85% by mole or higher, more preferably90% by mole or higher, particularly 95% by mole or higher. A % isotacticpentad referred herein is a % isotactic moiety in a triad unitdetermined by ¹³C-NMR, and is a value obtained as a ratio of the signalintensity of 21.7 to 22.5 ppm to the total signal intensity of 19.8 to22.5 ppm. ¹³C-NMR is determined in the manner similar to that employedfor determining the comonomer content (a) and the stereoregularity index(P) of a copolymer (A).

A copolymer of propylene with other α-olefin may for example be anethylene/propylene copolymer, an ethylene/1-butene/propylene copolymeror a 1-butene/propylene copolymer. A preferred ethylene/propylenecopolymer may for example be one described in JP-A-8-288052 orJP-A-8-313210.

A preferred ethylene/1-butene/propylene copolymer may for example be onedescribed in JP-A-9-209210 or JP-A-9-222356. Each of these copolymers ofpropylene and other α-olefins is characterized by a highstereoregularity of a propylene chain and a higher crystallinity inspite of a low melting point.

The melt index of a propylenic polymer (B) is preferably 0.1 to 100g/min. A propylenic polymer (B) having a crystallization temperaturedetermined by a differential scanning calorimeter which is lower thanthat of a copolymer (A) fails to obtain the moldability-improving effectwhich is an objective of the present invention.

An inventive propylenic resin should consist of 55 to 99 parts by weightof a copolymer (A) and 45 to 1 part(s) by weight of a propylenic polymer(B). A copolymer (A) content less than 55 parts by weight results in aninsufficient ability of improving the low temperature heat sealperformance. A propylenic polymer (B) content less than 1 part by weightresults in no moldability-improving effect. It is preferred to combine65 to 98 parts by weight of a copolymer (A) with to 2 parts by weight ofa propylenic polymer (B). It is further preferred to combine 75 to 95parts by weight of a copolymer (A) with 25 to 5 parts by weight of apropylenic polymer (B).

An inventive propylenic resin is preferred when the crystallizationtemperature (Tca ° C.) of a copolymer (A) and the crystallizationtemperature (Tcb ° C.) of a propylenic polymer (B), as determined by adifferential scanning calorimetry, are in the relationship representedby the following formula:

Tcb−Tca≦20  (1);

more preferably by the following formula:

Tcb−Tca≧30  (6); and,

most preferably by the following formula:

Tcb−Tca≧40  (7).

A small difference in the crystallization temperature between acopolymer (A) and a propylenic polymer (B) results in a lowmoldability-improving effect.

An inventive propylenic resin is preferred when a propylenic polymer (B)has the melting point (Tmb ° C.) and the crystallization temperature(Tcb ° C.), as determined by a differential scanning calorimetry, are inthe relationship represented by the following formula:

Tmb−Tcb≦50  (8);

more preferably by the following formula:

Tmb−Tcb≦45  (9); and,

most preferably by the following formula:

Tmb−Tcb≦40  (10).

A propylenic polymer (B) having a smaller difference between the meltingpoint and the crystallization temperature may have a smaller adverseeffect on the low temperature heat seal performance.

An inventive propylenic resin is preferred when it satisfies, upon beingsubjected to a temperature-raising fractional chromatography, thefollowing requirements (1), (2) and (3):

(1) when the main elution peak temperature is Tp, the amount (W(H)p) ofthe components dissolved out within the temperature range from (Tp−5) °C. to (Tp+5) ° C. is 65% by weight or more;(2) the amount (W(H)0) of the components dissolved out at 0° C. or loweris 3% by weight or less; and,(3) the amount (W(H)10) of the components dissolved out at Tp+10° C. orhigher is 1 to 45% by weight, based on the total weight.

A more preferred W(H)p is 70% by weight or higher. A further preferredW(H)p is 75% by weight or higher. A particularly preferred W(H)p is 80%by weight or higher. A value of W(H)p less than 65% by weight makes thelow temperature heat seal performance disadvantageously insufficient. Amore preferred W(H)0 is 1% by weight or less. A further preferred W(H)0is 1.5% by weight or less. A value of W(H) exceeding 3% by weightresults in a disadvantageously reduced anti-blocking ability.

A more preferred W(H)10 is 2 to 35% by weight. A further preferredW(H)₁₀ is 3 to 25% by weight. A particularly preferred W(H)₁₀ is 4 to20% by weight. A value less than 1% by weight may cause a poor moldingphenomenon, while one exceeding 45% by weight makes the low temperatureheat seal performance disadvantageously insufficient.

An inventive propylenic resin is preferred when the peak top temperatureon the side of the maximum temperature on the crystallization curve, asdetermined by a differential scanning calorimetry, is 85° C. or higher.

A more preferable peak top temperature is 90° C. or higher. A furtherpreferable peak top temperature is 95° C. or higher. A particularlypreferable peak top temperature is 100° C. or higher. A peak toptemperature below 85° C. results in a lower moldability-improvingeffect.

An inventive propylenic resin is preferred when the peak top temperatureon the side of the minimum temperature on the crystallization curve, asdetermined by a differential scanning calorimetry, is 150° C. or lower.

A more preferable peak top temperature is 140° C. or lower. A furtherpreferable peak top temperature is 130° C. or lower. A particularlypreferable peak top temperature is 120° C. or lower. A peak toptemperature exceeding 150° C. results in an insufficient low temperatureheat seal performance.

[4][Method for Producing Resins and Films]

In a propylenic resin according to the invention, a copolymer (A′) or(A′) can be obtained by a polymerization in the manner described inExamples, which is not limiting, and any method for producing acopolymer specified above may be employed.

A catalyst employed preferably in the production is a metallocenecatalyst obtained by combining a metallocene-based transition metalcompound with an organic aluminium compound or a boron compound. In thiscontext, a metallocene-based transition metal compound may for examplebe a compound of a transition metal selected from Group IVB, such astitanium, zirconium and hafnium, to which one or two cyclopentadienyl,substituted cyclopentadienyl, indenyl, substituted indenyl,tetrahydroindenyl, substituted tetrahydroindenyl, fluorenyl orsubstituted fluorenyl, groups are bound, or to which two of these groupscrosslinked covalently to each other are bound, and which furthercontains hydrogen atom, oxygen atom, halogen atom, alkyl, alkoxy, aryl,acetylacetonato, carbonyl group, nitrogen-, oxygen-, sulfur-,phosphorus-silicon-containing ligand.

An organic aluminium compound may be any of various aluminoxanecompounds. One preferred particularly is methylaluminoxane. Otherwise,an organic aluminium compound such as trimethylaluminium,triethylaluminium, triisobutylaluminium and the like may be used incombination.

A boron compound can preferably be used as an ionizing agent. Such boroncompound may for example be a trialkyl-substituted ammonium salt such astriethylammonium tetrapgenylborate, or an N,N-dialkylanilinium salt suchas N,N-dimethyltetraphenylborate, a phenylboron compound such astrispentafluorophenylboron and the like.

Such metallocene catalyst and/or an organic aluminium compound may beemployed also as being supported on a carrier.

In such case, a carrier may for example be an organic compound such asstyrene as well as an inorganic compound such as silica, alumina and thelike.

It is also possible that a small amount of α-olefin such as ethylene,propylene, 1-butene, an α-olefin having 5 or more carbon atoms and thelike is subjected to a preliminary polymerization before use.

A copolymerization of propylene and ethylene or an α-olefin having 4 to20 carbon atoms, i.e., a component (A′) or a copolymerization ofpropylene and an α-olefin having 5 or more carbon atoms, i.e., acomponent (A) may not particularly be limited, and may be a bulkpolymerization, a solution polymerization, a vapor phase polymerization,a suspension polymerization and the like, and may be performed as abatch process or a continuous process.

A method for feeding each monomer to a reaction system is notparticularly limited, and various methods can be employed. The monomerratio in a reaction system may not necessarily be constant always, andrespective monomers may be fed at a certain ratio, or such ratio mayvary depending on the timings of feeding. A certain monomer may be addedportionwise considering the copolymer reactivity ratio. Alternatively, agas mixture having a constant monomer ratio is introduced continuouslyto a reaction system, from which an excessive gas is removed using aexhaustion valve, whereby maintaining a constant monomer ratio in thereaction system. Hydrogen is also used as a molecular weight adjustingagent.

A polymerization condition is not particularly limited and may besimilar to that employed in a known method. For example, thepolymerization temperature is usually −50 to 250° C., preferably 0 to150° C. The reaction pressure is atmospheric pressure to 300 kg/cm² g.The polymerization time is 1 minute to about 10 hours.

In a propylenic resin according to the invention, a propylenic polymer(B′) or (B) can be obtained by a polymerization in the manner describedin Examples, which is not limiting, and any method for producing apropylenic polymer specified above may be employed.

A catalyst employed preferably is a catalyst formed from a solidcatalyst component whose essential component is magnesium, titanium andhalogen, an organic metal compound catalyst component such as an organicaluminium compound, and an electron donor compound catalyst componentsuch as a silane compound. In addition, a metallocene-based transitionmetal compound described above combined with an organic aluminiumcompound, a borane compound and the like, which is referred to as ametallocene catalyst, may also be employed preferably.

A polymerization condition is not particularly limited and may besimilar to that employed in a known method. For example, thepolymerization temperature is 20 to 150° C., and the reaction pressureis atmospheric: pressure to 40 kg/cm². The polymerization time is 1minute to about 10 hours. Hydrogen is also used as a molecular weightadjusting agent. A comonomer such as ethylene, 1-butene, an α-olefinhaving 5 or more carbon atoms and the like may be copolymerized asdesired.

An inventive propylenic resin can be obtained by incorporating acopolymer (A′) or (A) with a propylenic polymer (B′) or (B), in a mannerwhich is not limited. While the examples described later employ theseparate productions of a copolymer (A′) or (A) and a propylenic polymer(B′) or (B) followed by a incorporating step, to which no limitation ismade. For example, the first step reactor is used to polymerize apropylenic polymer (B), which is then transferred to the second stepreactor, in which propylene and an α-olefin having 5 or more carbonatoms are polymerized. In such case, the catalyst in the second step isnot necessarily identical to that in the first step, and any suitablecatalysts may be selected.

To a propylenic resin in this invention, customary additives such asantioxidant, neutralizing agent, slipperiness-imparting agent,anti-blocking agent and anti-static agent may be incorporated asdesired.

An inventive propylenic resin may be molded into a film using a meltextrusion molding method. For example, in a T die cast film-formingprocess, it can be used preferably to form a film having a thickness of10 to 500 μm even in a fast film-forming condition at a haul-off speedof 50 mm/min or even higher. It can also be employed preferably as atleast one layer in a laminated film production by means of aco-extrusion film-forming process.

While as a film forming method a T die cast film-forming process inwhich a large film-forming machine is used to effect a high speedfilm-forming is employed preferably, no limitation is made thereto, andwith any film-forming process capable of producing a film by a meltextrusion molding, an inventive propylenic resin can preferably beemployed.

[VIII] Eighth Invention

The eighth invention relates to a novel transition metal compound havinga double crosslinking ligand useful as an olefin polymerizationcatalyst, an olefin polymerization catalyst comprising a compoundcapable of forming an ionic complex by reacting said transition metalcompound and a method for producing an olefinic polymer. An inventivetransition metal compound [I], an olefin polymerization catalyst [II]comprising a compound capable of forming an ionic complex by reactingsaid transition metal compound, and a method for producing an olefinicpolymer [III] are detailed below.

[I] Transition Metal Compound

An inventive transition metal compound is a double crosslinking compoundof a transition metal of Group 3 to Group or of lanthanoids in theperiodic table, which has the structure represented by Formula (VIII):

wherein each of A³ and A⁴ denotes a crosslinking consisting of Group XIVmetal (C, Si, Ge, Sn) and may be same to or different from each other,X⁴ denotes a σ-binding or 7-binding ligand, and when two or more X⁴ arepresent they may be same or different, Y⁵ is a Lewis base and when twoor more Y⁵ are present they may be same or different, and each Y⁵ may becrosslinked with other Y⁵ or X⁴, q is an integer of 1 to 5 andrepresents [(valency of M3)−2], r is an integer of 0 to 3, each of R²¹to R³⁰ denotes a hydrogen atom, a halogen atom, a hydrocarbon grouphaving 1 to 20 carbon atom(s), a silicon-containing group and aheteroatom-containing group, and M³ denotes a metal element of Group 3to Group 10 or of lanthanoids in the periodic table.

In Formula (VIII) shown above, each of A³ and A⁴ forms a crosslinkinggroup consisting of Group IVX element (C, Si, Gen) and may be same to ordifferent from each other. A³ or A⁴ may for example be a crosslinkinggroup represented by Formula (VIV):

wherein E denotes C, Si, Ge, Sn, each of R³¹ and R³² denotes a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atom(s)or a halogen-containing hydrocarbon group having 1 to 20 carbon atom(s),and each may be same to or different from each other, or the both may betaken together to form a ring.

A halogen atom in Formula (VIV) may for example be a chlorine, fluorine,bromine or iodine atom. Examples of a hydrocarbon group having 1 to 20carbon atom(s) are an alkyl group such as methyl, ethyl, propyl, butyl,hexyl, cyclohexyl, octyl groups and the like, an alkenyl group such asvinyl, propenyl, cyclohexenyl groups and the like; an arylalkyl groupsuch as benzyl, phenylethyl, phenylpropyl groups and the like; and anaryl group such as phenyl, tolyl, dimethylphenyl, trimethylphenyl,ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl,anthracenyl, phenanthnyl groups and the like. Among those listed above,an alkyl group such as methyl, ethyl, propyl groups and the like and anaryl group such as phenyl group are preferred. A halogenated hydrocarbonhaving 1 to 20 carbon atom(s) may for example be one of the hydrocarbongroups listed above which is substituted with a halogen atom. Amongthese, those preferred are a halogenated alkyl group such astrifluoromethyl, trichloromethyl groups and the like.

A crosslinking group consisting of a carbon atom in Formula (VIV) mayfor example be methylene, dimethylmethylene group; an alkylidene groupsuch as ethylidene, propylidene, isopropylidene, cyclohexylidene and thelike; as well as 1,1-cyclohexylene and vinylidene groups. A crosslinkinggroup consisting of a silicon atom may for example be an alkylsilylenegroup such as methylsilylene, dimethylsilylene, diethylsilylene,di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene andthe like; an alkylarylsilylene group methylphenylsilylene,ethylphenylsilylene and the like; and arylsilylene group such asdiphenylsilylene, di(p-tolyl)silylene, di(p-chlorophenyl)silylene andthe like. A crosslinking group consisting of a germanium atom may forexample be a germylene group obtained by replacing a silicon atom in acrosslinking group consisting of a silicon atom listed above with agermanium atom. A crosslinking group consisting of a tin atom may forexample be a stannylene group obtained by replacing a silicon atom in acrosslinking group consisting of a silicon atom listed above with a tinatom. One preferred as A³ or A⁴ is a crosslinking group consisting of acarbon atom or a crosslinking group consisting of a silicon atom.

X⁴ is a σ-binding or π-binding ligand, and such σ-binding ligand may forexample be a halogen atom, a hydrocarbon group having 1 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxygrouphaving 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms,a silicon-containing group having 1 to 20 carbon atoms, a phosphidegroup having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbonatoms, a sulfoxide group having 1 to 20 carbon atoms and an acyl grouphaving 1 to 20 carbon atoms, among which a halogen atom and ahydrocarbon group having 1 to 20 carbon atoms are preferred. A halogenatom and a hydrocarbon group having 1 to 20 carbon atoms may be thosedescribed above. An alkoxy group having 1 to 20 carbon atoms may forexample be an alkoxy group such as methoxy, ethoxy, propoxy, butoxygroups and the like; and an aryloxy group such as phenoxy,methylphenoxy, dimethylphenoxy, naphthoxy groups and the like. Anaryloxy group having 6 to 20 carbon atoms may for example bephenylmethoxy, phenylethoxy groups and the like. An amide group having 1to 20 carbon atoms may for example be an alkylamide group such asdimethylamide, diethylamide, dipropylamide, dibutylamide,dicyclohexylamide, methylethylamide groups and the like, an alkenylamidegroup such as divinylamide, dipropenylamide, dicyclohexenylamide groupsand the like; an arylalkylamide group such as dibenzylamide,phenylethylamide, phenylpropylamide groups and the like; and arylamidegroup such as diphenylamide, dinaphtylamide groups and the like. Asilicon-containing group having 1 to 20 carbon atoms may for example bea monohydrocarbon-substituted silyl group such as methylsilyl,phenylsilyl groups and the like; a dihydrocarbon-substituted silyl groupsuch as dimethylsilyl, diphenylsilyl groups and the like; atrihydrocarbon-substituted silyl group such as trimethylsilyl,triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,dimethylphenylsilyl, methylphenyldisilyl, tritolylsilyl,trinaphthylsilyl groups and the like; a silyl ether group of ahydrocarbon-substituted silyl group such as trimethylsilylether group; asilicon-substituted alkyl group such as trmethylsilylmethyl group; and asilicon-substituted aryl group such as trimethylsilylphenyl group andthe like. Among those listed above, trimethylsilyl,phenethyldimethylsilyl groups are preferred. A sulfide group having 1 to20 carbon atoms may for example be an alkylsulfide group such asmethylsulfide, ethylsulfide, propylsulfide, butylsulfide, hexylsulfide,cyclohexylsulfide, octylsulfide groups and the like and analkenylsulfide group such as vinylsulfide, propenyl sulfide,cyclohexenylsulfide groups and the like; an arylalkylsulfide group suchas benzylsulfide, phenylethylsulfide, phenylpropylsulfide groups and thelike; and an arylsulfide group such as phenylsulfide, tolylsulfide,dimethylsulfide, trimethylphenylsulfide, ethylphenylsulfide,propylphenylsulfide, biphenylsulfide, naphthylsulfide,methylnaphthylsulfide, anthracenylsulfide, phenanthnylsulfide groups andthe like. A sulfoxide group having 1 to 20 carbon atoms may for examplebe an alkylsulfoxide group such as methylsulfoxide, methylsulfoxide,propylsulfoxide, butylsulfoxide, hexylsulfoxide, cyclohexylsulfoxide,octylsulfoxide groups and the like and an alkenylsulfoxide group such asvinylsulfoxide, propenylsulfoxide, cyclohexenylsulfoxide groups and thelike; an arylalkylsulfoxide group such as benzyl sulfoxide,phenylethylsulfoxide, phenylpropylsulfoxide groups and the like; and anarylsulfoxide such as phenylsulfoxide, tolylsulfoxide,dimethylphenylsulfoxide, trimethylphenylsulfoxide, ethylphenylsulfoxide,propylphenylsulfoxide, biphenylsulfoxide, naphthylsulfoxide,methylnaphthylsulfoxide, anthracenylsulfoxide, phenanthnylsulfoxidegroups and the like. An acyl group having 1 to 20 carbon atoms may forexample be an alkylacyl group such as formyl, acethyl, propionyl,butyryl, valeryl, palmitoyl, thearoyl, oleoyl groups and the like; anarylacyl group such as benzoyl, toluoyl, salicyloyl, cinnamoyl,naphthoyl, phthaloyl groups and the like; oxalyl, malonyl and succinylgroups derived from dicarboxylic acids such as oxalic acid, malonic acidand succinic acid, respectively, and the like.

A π-binding ligand may for example be a conjugated diene bond-carryingcompound having 4 to 20 carbon atoms, a non-conjugated dienebond-carrying compound having 5 to 20 carbon atoms and the like. Aconjugated diene bond-carrying compound having 4 to 20 carbon atoms mayfor example be 1,3-butadiisoprene, chloroprene, 1,3-pentadiene,1,3-hexadiene, 1,3,5-hexatriene, 1,3-heptadiene, 1,3,6-heptatriene,1,4-diphenylbutadiene and the like. A non-conjugated diene bond-carryingcompound having 5 to 20 carbon atoms may for example be 1,4-pentadiene,1,4-hexadiene and the like.

Characteristically, a σ-binding ligand in X⁴ gives an enhancedreactivity with M³. On the other hand, a n7-binding ligand gives anincreased activity.

Y⁵ is a Lewis base and when two or more Y5 are present they may be sameor different. Each Y5 may be crosslinked with other Y⁵ or X⁴. Y⁵ mayoptionally be crosslinked with a cyclopentadienyl ring in Formula(VIII). Examples of Y⁵ are amines, ethers, phosphines, thioethers andthe like. Amines may for example be an amine having 1 to 20 carbonatoms, and typically an alkylamine such as methylamine, ethylamine,propylamine, butylamine, cyclohexylamine, methylethylamine,dimethylamine, diethylamine, dipropylamine, dibutylamine,dicyclohexylamine, methylethylamine and the like and an alkenylaminesuch as vinylamine, propenylamine, cyclohexenylamine, divinylamine,dipropenylaine, dicyclohexenylamine and the like; an arylalkylamine suchas phenylamine, phenylethylamine, phenylpropylamine and the like; andarylamine such as diphenylamine, dinaphthylamine and the like. Ethersmay for example be an aliphatic monoether compound such as methylether,ethylether, propylether, isopropylether, butylether, isobutylether,n-amylether, isoamylether and the like; an aliphatic mixed ethercompound such as methylethylether, methylpropylether,methylisopropylether, methyl-n-amylether, methylisoamylether,ethylpropylether, ethylisopropylether, ethylbutylether,ethyliobutylether, ethyl-n-amylether, ethylisoamylether and the like; analiphatic unsaturated ether compound such as vinylether, allylether,methylvinylether, methylallylether, ethylvinylether, ethylallylether andthe like; an aromatic ether compound such as anisol, phenethol,phenylether, benzylether, phenylbenzylether, α-naphthylether,β-naphthylether and the like, as well as a cyclic ether compound such asethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran,tetrahydropyrane, dioxane and the like. An example of the phosphines maybe a phosphine having 1 to 20 carbon atoms. Those included typically arean alkylphosphine including a monohydrocarbon-substituted phosphine suchas methylphosphine, ethylphosphine, propylphosphine, butylphosphine,hexylphosphine, cyclohexylphosphine, octylphosphine and the like; adihydrocarbon-substituted phosphine such as dimethylphosphine,diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine,dicyclohexylphosphine, dioctylphosphine and the like; atrihydrocarbon-substituted phosphine such as dimethylphosphine,triethylphosphine, tripropylphosphine, tributylphosphine,trihexylphosphine, tricyclohexylphosphine, trioctylphosphine and thelike and a monoalkenylphosphine such as vinylphosphine,propenylphosphine, cyclohexenylphosphine and the like as well as adialkenyl phosphine whose hydrogen atoms on the phosphorus were replacedwith two alkenyl groups; a trialkenyl phosphine whose hydrogen atoms onthe phosphorus were replaced with three alkenyl groups; anarylalkylphosphine such as benzylphosphine, phenylethylphosphine,phenylpropylphosphine and the like; a diarylalkyl phosphine or anaryldialkylphosphine whose hydrogen atoms on the phosphorus werereplaced with three aryl or alkenyl groups; phenylphosphine,tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine,ethylphenylphosphine, propylphenylphosphine, biphenylphosphine,naphthylphosphine, methylnaphthylphosphine, anthracenylphosphine,phenanthracenyl phosphine; a di(alkylaryl)phosphine whose hydrogen atomson the phosphorus were replaced with 2 aklkylaryl groups; atri(alkylaryl)phosphine whose hydrogen atoms on the phosphorus werereplaced with 3 aklkylaryl groups, and the like. An example of thethioethers may be a sulfide mentioned above.

Each of R²¹ to R³⁰ denotes a hydrogen atom, a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms, a silicon-containinggroup and a heteroatom-containing group, and a halogen atom may forexample be chlorine, fluorine, bromine, iodine atoms. A hydrocarbongroup having 1 to 20 carbon atoms may for example be an alkyl group suchas methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl groups and thelike and an aryl group such as phenyl, naphthyl groups and the like; anarylalkyl group such as benzyl, phenylethyl, phenylpropyl groups and thelike; an alkylaryl group such as tolyl, xylyl groups and the like. Asilicon-containing group may for example be a silicon-containing grouphaving 1 to 20 carbon atoms, typical examples of which aretrimethylsilyl, trimethylsilylmethyl, triphenylsilyl groups and thelike. A heteroatom-containing group may for example be aheteroatom-containing group having 1 to 20 carbon atoms, typicalexamples of which are a nitrogen-containing group such as dimethylamino,diethylamino, diphenylamino groups and the like, a sulfur-containinggroup such as phenylsulfide, methylsulfide groups and the like; aphosphorus-containing group such as dimethylphosphino, diphenylphosphinogroups and the like; an oxygen-containing group such as methoxy, ethoxy,phenoxy groups and the like. Those employed preferably as R²¹ to R³⁰ area hydrogen atom or a hydrocarbon group having 1 to carbon atoms.

M3 denotes a metal element of Group 3 to Group 10 or of lanthanoids inthe periodic table, and is typically titanium, zirconium, hafnium,vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanoidmetals. A metal element of Group IV in the periodic table is preferableas M³ since it gives a higher activity.

A preferred representative of a transition metal compound represented byFormula (VIII) shown above is one wherein A³ and A⁴ denotes acrosslinking group consisting of a carbon atom or a silicon atom whichmay be same to or different from each other; X⁴ denotes a σ-binding or7-binding ligand, and when two or more X⁴ are present they may be sameor different; Y⁵ is a Lewis base and when two or more Y⁵ are presentthey may be same or different; each Y⁵ may be crosslinked with other Y⁵or X⁴; q is an integer of 1 to 5 and represents [(valency of M³)−2], ris an integer of 0 to 3, each of R²¹ to R³⁰ denotes a hydrogen atom or ahydrocarbon group having 1 to 20 carbon atoms; and M³ denotes a metalelement of Group IV in the periodic table.

A transition metal compound represented by Formula (VIII) shown above,when those of Group IV in the periodic table are exemplified, includes(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-ethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-isopropylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(4,7-dimethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-phenylmethylsilylene)(2,1′-phenylmethylsilylene)bis(indenyl)zirconiumdichloride,(1,2′-phenylmethylsilylene)(2,1′-phenylmethylsilylene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-isopropylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-trimethylsilylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)bis(3-phenylindenyl)zirconiumdichloride, (1,2′-dimethylsilylene)(2,1′-methylene)bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)bis(3-isopropylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-methylene)bis(3-trimethylsilylindenyl)zirconiumdichloride, (1,2-diphenylsilylene)(2,1′-methylene)bis(indenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)bis(3-methylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)bis(3-n-butylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)bis(3-trimethylsilylmethylindenyl)zirconiumdichloride,(1,2′-diphenylsilylene)(2,1′-methylene)bis(3-trimethylsilylindenyl)zirconiumdichloride as well as the compounds obtained by replacing zirconium inthe compounds listed above with titanium or hafnium, while they are notlimiting. An analogous compound of a metal element of Groups other thanGroup IV or of lanthanoids. Preferably, a compound of a transition metalof Group IV in the periodic table, especially of zirconium is employed.

[II] Olefin Polymerization Catalyst

An inventive olefin polymerization catalyst consists of (A) a transitionmetal element of Group 3 to Group 10 or of lanthanoids in the periodictable represented by Formula (VIII) and (B) a compound capable offorming an ionic complex by reacting with a transition metal compound asa component (A), optionally with (C) an organic aluminium compound.

In an inventive polymerization catalyst, a component (A) and a compoundcapable of forming an ionic complex by reacting with a transition metalcompound as a component (A).

One exemplified preferably as a component (B) is (B-1) an ionic compoundcapable of forming an ionic complex by reacting with a transition metalcompound as a component (A), (B-2) an aluminoxane, or (B-3) a Lewisacid, because of its high polymerization activity and low catalyst cost.

A component (B-1) described above may be any ionic compound capable offorming an ionic: complex by reacting with a transition metal compoundas a component (A), and may for example be one exemplified as acomponent (B-1) in the first invention.

An ionic compound, which is a component (B-1), capable of forming anionic complex by reacting with a transition metal compound as acomponent (A) may be employed alone or in a combination with one ormore.

An aluminoxane as a component (B-2) may be any substance such as thosedescribed in the first invention as a component (B-2). Such aluminoxanemay be employed alone or in a combination with one or more.

A Lewis acid as a component (B-3) is not particularly limited, and maybe an organic compound or a solid inorganic compound. An organiccompound employed preferably is a boron compound, an aluminium compoundand the like, while an inorganic compound employed preferably is amagnesium compound, an aluminium compound and the like, because of theirability of forming an active center efficiently. Such aluminium compoundmay for example be bis(2,6-di-t-butyl-4-methylphenoxy)aluminium methyl,(1,1-bi-2-naphthoxy)aluminium methyl and the like, while a magnesiumcompound may for example be magnesium chloride, diethoxymagnesium andthe like, and an aluminium compound may for example be aluminium oxide,aluminium chloride and the like, and a boron compound may for example betriphenylboron, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron,tris[(4-fluoromethyl)phenyl]boron, trimethylboron, triethylboron,tri-n-butylboron, tris(fluoromethyl)boron, tris(pentafluoroethyl)boron,tris(nonafluorobutyl)boron, tris(2,4,6-trifluorophenyl)boron,tris(3,5-difluoro)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,bis(pentafluorophenyl)fluoroboron, diphenylfluoroboron,bis(pentafluorophenyl)chloroboron, dimethylfluoroboron,diethylfluoroboron, di-n-butylfluoroboron,pentafluorophenyldifluoroboron, phenyldifluoroboron,pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron,n-butyldifluoroboron and the like.

Such Lewis acid may be employed alone or in a combination with one ormore.

The molar ratio of a catalyst component (A) to a catalyst component (B)when employing a compound (B-1) as a catalyst component (B) ispreferably 10:1 to 1:100, more preferably 2:1 to 1:10, and a ratiodeparting from this range is not advantageous industrially because of anincreased catalyst cost per unit weight of a polymer. When a compound(B-2) is employed, the molar ratio is preferably 1:1 to 1:1000000, morepreferably 1:10 to 1:10000. A ratio departing from this range is notadvantageous industrially because of an increased catalyst cost per unitweight of a polymer.

The molar ratio of a catalyst component (A) to a catalyst component(B-3) is preferably 10:1 to 1:2000, more preferably 5:1 to 1:1000,particularly 2:1 to 1:500, and a ratio departing from this range is notadvantageous industrially because of an increased catalyst cost per unitweight of a polymer. As a component (B), any one of, or, a combinationof two or more of components (B-1), (B-2) and (B-3) may be employed.

A polymerization catalyst according to the invention may comprise asmain components a component (A) and a component (B) described above, ormay comprise as main components a component (A), a component (B) and anorganic aluminium compound (C).

An organic aluminium compound as a component (C) may be one listed as acomponent (C) in the first invention.

Such organic aluminium compound may be employed alone or in acombination of two or more.

The molar ratio of a catalyst component (A) to a catalyst component (C)is preferably 1:1 to 1:10000, more preferably 1:5 to 1:2000,particularly 1:10 to 1:1000. By employing a catalyst component (C), thepolymerization activity per unit weight of a transition metal can beincreased, but a too excessive amount, especially one departing from therange specified above, is of no use, and results in a large amount ofresidue remaining in a polymer, while a too small amount may fail toobtain a sufficient catalyst activity.

Upon contact or after contact between components in this invention, apolymer such as polyethylene, polypropylene and the like, or aninorganic oxide such as silica, alumina and the like, is allowed toexist simultaneously or to be in contact. A support on a carrier may beeffected preferably as a support on a polymer, and such polymericcarrier has a particle size of 1 to 300 μm, preferably 10 to 200 μm,more preferably 20 to 100 μm. A particle size smaller than 1 μm resultsin increased microparticles in a polymer, while one exceeding 300 μmresults in increased coarse particles in a polymer, which leads to aproblematic reduction in the bulk density and a plugging of a hopper ina manufacturing process. The specific surface area of a carrier whenemployed as discussed above is 1 to 1,000 m²/g, preferably 50 to 500m²/gm, and a micropore void volume is 0.1 to 5 m³/g, preferably 0.3 to 3m³/g.

A contact may be effected in an atmosphere of an inert gas such asnitrogen, and in a hydrocarbon such as pentane, hexane, heptane,toluene, xylene and the like. While an addition or a contact of eachcomponent may of course be effected at a polymerization temperature, atemperature of −30° C. to a boiling point of a solvent, especially roomtemperature to a boiling point of a solvent is preferred.

[III] Method for Producing Olefin Polymer

An inventive method for producing an olefin polymer is a method forproducing a polymer wherein

An olefin is homopolymerized or copolymerized in the presence of anolefin-polymerizing catalyst obtained by bringing (A) a transition metalelement of Group 3 to Group or of lanthanoids in the periodic tablerepresented by Formula (VIII) into contact with (B) a compound capableof forming an ionic complex by reacting with a transition metal compoundas a component (A) optionally together with (C) an organic aluminiumcompound. As an organic aluminium compound (C), a compound representedby Formula (VII) shown above is employed, and is preferably atrialkylaluminium compound. Those particularly preferred aretrimethylaluminium and triisobutylaluminium. In an inventive method forproducing an olefin polymer, an organic aluminium compound (C) may beemployed as being brought into contact preliminarily with a component(A) and/or a component (B), or may be introduced first 0* into a reactorand then brought into contact with a component (A) and a component (B).The amount of a component (C) employed is similar to that describedabove in the section of the olefin polymerization catalyst. According toan inventive method for producing an olefin polymer, a polymerizationcatalyst described above is used preferably to effect ahomopolymerization of an olefin or a copolymerization of an olefin withother olefins and/or other monomers (a copolymerization betweendifferent olefins, a copolymerization between olefins and othermonomers, or a copolymerization between different olefins together withother monomers).

While such olefin is not particularly limited, an α-olefin having 2 to20 carbon atoms is preferred. Such α-olefin may for example be α-olefinssuch as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene,3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene,3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane and thelike, diens such as 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, andthe like, a halogenated α-olefin such as hexafluoropropene,tetrafluoroethylene, 2-fluoropropene, fluororthylene,1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene,3,4-dichloro-1-butene and the like, cyclic olefins such as cyclopentene,cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene,5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene and thelike, styrenic substances including alkylstyrenes such as styrene,p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene,p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene,o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene,m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene,2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene and thelike, alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene,m-methoxystyrene and the like, halogenated styrenes such asp-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene,m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene,o-fluorostyrene, o-methyl-p-fluorostyrene and the like, as well astrimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like.Other olefins described above may appropriately selected from theolefins listed above.

In this invention, any one of, or a combination of two or more of theolefins listed above may be employed. When two or more olefins iscopolymerized, any combination of the olefins listed above may beemployed.

Also in this invention, the olefins listed above may be copolymerizedwith other monomers, and such monomers are linear diolefins such asbutadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and the like,polycyclic olefins such as norbornene,1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-norborneneand the like, cyclic olefins such as norbornadiene,5-ethylidenenorbornene, 5-vinylnorbornene, dicyclopentadiene and thelike, unsaturated esters such as ethyl acrylate, methyl methacrylate andthe like.

In this invention, one preferred particularly as such olefin ispropylene.

A method for polymerizing olefins is not particularly limited, and maybe a slurry polymerization, a solution polymerization, a vapor phasepolymerization, a bulk polymerization, a suspension polymerization.

When a polymerization solvent is employed, such solvent may for examplebe a hydrocarbon and a halogenated hydrocarbon such as benzene, toluene,xylene, n-hexane, n-heptane, cyclohexane, methylene chloride,chloroform, 1,2-dichloroethane, chlorobenzene and the like. Any one of,or a combination of two or more of those listed above may be employed. Acertain monomer subjected to a polymerization may be used also as asolvent.

The amount of a catalyst employed in a polymerization reaction isselected so that a component [A] is within the range usually of 0.5 to100 micromoles, preferably 2 to 25 micromoles per 1 liter of a solvent,for the purpose of advantageous polymerization activity and reactorefficiency.

A polymerization condition involves a polymerization pressure usually ofatmospheric pressure to 2000 kg/cm²G. The reaction temperature isusually −50 to 250° C. The molecular weight of a polymer may be adjustedby appropriately selecting the types and amounts of respective catalystcomponents, and the polymerization temperature, or by introducinghydrogen.

Also in a polymerization process of an olefin according to theinvention, a catalyst described above is used to effect a preliminarypolymerization. Such preliminary polymerization can be effected bybringing a solid catalyst component into contact with a small amount ofan olefin, at a reaction temperature of −20 to 100° C., preferably −10to 70° C., particularly 0 to 50° C. While an inert hydrocarbon, analiphatic hydrocarbon, an aromatic hydrocarbon or a monomer is employedas a solvent for this preliminary polymerization, an aliphatichydrocarbon is particularly preferred. This preliminary polymerizationmay be effected also in the absence of a solvent. In a preferablyadjusted condition, a preliminary polymerization product has anintrinsic viscosity [η] (at 135° C. in decalin) of 0.2 dl/g, preferably0.5 dl/g, and an amount of a preliminary polymerization product per 1millimole of a transition metal component in a catalyst is 1 to 10,000g, preferably 10 to 1,000 g.

The present invention is further described in the following the exampleswhich is not intended to restrict the invention.

[First Invention]

A method for evaluating a propylenic polymer and a method for evaluatinga film are described below.

(A) Method for Evaluating Resin Characteristics (1) Intrinsic Viscosity[η]

An automatic viscometer model VMR-053 available from RIGOSHA (KK) wasused in a decalin solvent at 135° C.

(2) Molecular Weight Distribution (Mw/Mn)

Measurement was made in accordance with the method described in thedetailed description of the invention.

(3) % Isotactic Pentad and % Abnormal Insertion

Measurement was made in accordance with the method described in thedetailed description of the invention.

(4) Melting Point (Tm) and Crystallization Temperature (Tc)

Using a differential scanning calorimeter (Perkin Elmer, DSC-7), 10 mgof a sample was fused for 3 minutes at 230° C. under a nitrogenatmosphere and then the temperature was lowered to 0° C. at the rate of10° C./minutes. The peak top of the maximum peak in the crystallizationexothermic curve obtained during this course was regarded as thecrystallization temperature. After holding at 0° C. for 3 minutes, thetemperature was raised at the rate of 10° C./minute to obtain a fusionendothermic curve, in which the peak top of the maximum peak wasregarded as the melting point.

(5) Boiling Ether Extraction

Soxlet extractor was used under the conditions specified below.

Extraction sample: 5 to 6 gState of sample: Powder (a pellet should be pulverized into a powderbefore use)Extraction solvent: DiethyletherExtraction duration: 10 hoursExtraction times: 180 times or moreCalculation of extract: As shown below

[Amount extracted into diethylether (g)]/Charged powder weight (g)]×100

(6) Temperature-Raising Fractional Chromatography (TREF)

A peak top temperature Tp (° C.) of a main elution peak in an elutioncurve, and an amount (% by weight based on the entire copolymer) of thecomponents which are dissolved out, instead of adsorbed onto a packing,at the TREF column temperature of 25° C. were obtained as describedbelow.

(a) Operating Procedure

A sample solution was introduced into a TREF column adjusted at 135° C.and then the temperature was lowered gradually at the lowering rate of5° C./hour to 25° C. to allow the sample to be adsorbed on the packing.Thereafter, the column temperature was raised at the raising rate of 40°C./hour to 135° C. to obtain an elution curve.

(b) Instruments

TREF column: Manufactured by GL SCIENCE, Silica gel column (4.6φ×150 mm)Flow cell: Manufactured by GL SCIENCE, pathlength 1 mm, KBr cellFeed pump: Manufactured by SENSHU KAGAKU, Pump Model SSC-3100Valve oven: Manufactured by GL SCIENCE, Oven model 554 (high temperaturetype)TREF oven: Manufactured by GL SCIENCEDual-system thermostat: Manufactured by RIKAGAKU KOGYO, Thermostat modelREX-C100Detector: Infrared detector for HPLC, Manufactured by FOXBORO CORP.,Model MIRAN 1A CVF10-way valve: Manufactured by VALCO, Electric valve

Loop: Manufactured by VALCO, 500 μL Loop (C) Operating Conditions

Solvent: o-DichlorobenzeneSample concentration: 7.5 g/LInjection volume: 500 μLPumping rate: 2.0 mL/minDetection wavenumber: 3.41 μmColumn packing: CHROMOSOLVE P (30 to 60 mesh)Column temperature deviation: Within ±0.2° C.

(7) Comonomer Unit α-Olefin Unit) Content (c(% by Mole)) in Copolymerand Stereoregularity Index (P(% by Mole))

A ¹³C NMR spectrum was obtained using Nippon Densi Model JNM-EX400¹³C-NMR device under the conditions specified below and calculation wasmade also as shown below.

Concentration: 220 mg/NMR Solvent 3 mlSolvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10% by volume)

Temperature: 130° C. Pulse gap: 45°

Pulse interval: 10 secondsNumber of cycles: 4000 times

(a) 1-Butene Unit

The 1-butene unit content (α(% by mole)) in the copolymer was obtainedin accordance with the following equation from the spectrum determinedby the ¹³C-NMR.

$\alpha = {\frac{\left( {{{I(2)}/2} + {I(4)}} \right)}{\left\{ {{I(1)} + {I(2)} + {I(3)} + {I(4)} + {2 \times {I(9)}}} \right\}} \times 100}$

Also in accordance with the following equation, a stereoregularity index(P(% by mole)) of the copolymer was obtained.

$P = {\frac{\left( {I(12)} \right)}{\left\{ {{I(12)} + {I(13)} + {I(14)}} \right\}} \times 100}$

wherein (1), (2) and the like represent the signals of a spectrum of acopolymer of propylene and 1-butene determined by ¹³C-NMR. I(1), I(2)and the like represent the respective signal intensities. The signals ofa spectrum of a copolymer of propylene and 1-butene determined by¹³C-NMR are indicated in the table shown below.

Instead of the signal intensity of a PPP chain Sαβ carbon, the signalintensity of a PPP chain Sαβ carbon (signal intensity of (9)) wasindicated as an alternative.

TABLE 1 Number Chemical shift Assignment 1 45.7-47.4 PP Sαα 2 43.0-44.9PB Sαα 3 42.3 PPP Sαα 4 40.3 BB Sαα 5 36.6 PPP Tαγ 6 36.0 PPP Sαβ andPPP Sαβ 7 35.5 B unit Tββ 8 31.6 PPP Tβγ 9 30.6 PPP Sαβ 10 28.6-29.8 Punit Tββ 11 27.8-28.4 B unit side chain methylene carbon 12 21.2-22.7Pββ PPP(mm), PPB(mm), BPB(mm) 13 20.6-21.2 Pββ PPP(mr), PPB(mr),BPB(mr), PPB(rr), BPB(rr) 14 19.8-20.6 Pββ PPP(rr) 15 17.6 Pαβ 16 17.2Pαγ 17 11.1 B unit side chain methyl carbon NOTE) B denotes a 1-buteneunit.

(8) Tensile Modulus

A propylenic polymer was press-molded to obtain a test piece, which wassubjected to the tensile test in accordance with JIS K-7113 under theconditions specified below.

Crosshead speed: 50 mm/min

Test piece form: JIS No. 2 dumb-bell test specimen, 1 mm in thickness

(9) Izod Impact Strength

Using a test piece having the thickness of 3 mm prepared as describedabove was subjected to the test in accordance with JIS K7110 at 23° C.

(10) Transparency

A test piece described above was evaluated visually.

The result was indicated as ◯ when the transparency was judged to besatisfactory, while it was indicated as Δ when judged to be somewhatpoor.

(11) Internal Haze

A propylenic polymer was press-molded to obtain a test piece whosethickness was 1 mm, and after applying a silicone oil (manufactured bySHINETSU SILICONE, KF56) onto the surface of the test piece, the hazewas determined in accordance with JIS K7105.

(B) Film-Forming Method

From a propylenic polymer composition obtained in Examples andComparatives described later, a film whose thickness was 50 μm wasformed using a 20 mmφ molding machine manufactured by TSUKADAJUKISEISATKUSHO under the molding conditions specified below.

T die exit resin temperature: 192° C.Haul-off speed: 6.0 m/minChill roll temperature: 40° C.Chill roll: Mirror

(C) Film Qualification

A film once formed was subjected to aging at 40° C. for 24 hoursfollowed by conditioning at a temperature of 23±2° C. and a humidity of50±10% for 16 hours or longer and then qualified at the same temperatureand humidity.

(1) Tensile Modulus

A tensile test was conducted under the conditions specified below inaccordance with JIS K-7127.

Crosshead speed: 500 mm/minLoad cell: 15 kgDirection: Machine direction

(2) Impact Resistance

Film impact tester manufactured by TOYOSEKI SEISAKUSHO was used togetherwith a ½ inch impact head to evaluate a impact destruction strength.

(3) Haze

A test was conducted in accordance with JIS K-7105.

(4) Heat Seal Temperature

A test was conducted in accordance with JIS Z-1707. The fusingconditions were as indicated below. The temperature of the heat seal barwas corrected as being read by a surface thermometer. After sealingfollowed by allowing to stand at room temperature overnight, the peelingstrength was determined by a type-T peeling method at the peeling speedof 200 mm/min at room temperature. The heat seal temperature wasobtained as a temperature at which the peeling strength was 300 g/15 mmby calculating on the basis of a curve of a seal strength vs peelingstrength.

Seal duration: 2 secondsSeal area: 15×10 mmSeal pressure: 5.3 kg/cm²GSeal temperature: Several temperatures over the range which include theheat seal temperature to be calculated later

Example I-1 [1] Catalyst Preparation (1) Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methyl indene)

Under nitrogen flow, 1.12 g (3.94 mmol) of(1,2′-ethylene)(2,1′-ethylene)-bis(indene) was dissolved in 50 ml ofanhydrous ether. After cooling to −78° C., 5.01 mL of a 1.57 mol/Lsolution of n-butyllithium in hexane (n-butyllithium: 7.87 mmol) wasadded dropwise over 30 minutes, and then the mixture was warmed to roomtemperature and stirred for 8 hours. The ether solvent was distilled offunder reduced pressure and the residue was washed with hexane to obtain1.12 g (3.02 mmol) of a dilithium salt as an ether adduct. Thisdilithium salt was dissolved in 50 mL of anhydrous tetrahydrofuran andcooled to −78° C. To this solution, 10 mL of a tetrahydrofuran solutioncontaining 0.42 mL (6.74 mmol) of methyl iodide was added dropwise over20 minutes, and the mixture was warmed to room temperature and stirredfor 8 hours. After distilling the solvent off under reduced pressure,the residue was extracted with ethyl acetate. This extract was washedwith water, and the organic phase was dried over anhydrous magnesiumsulfate and filtered, and the filtrate was evaporated to dryness underreduced pressure to obtain 0.87 g (2.78 mmol) of the desired substance,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindene) (Yield: 70.5%). Thissubstance was present as a mixture of the isomers with regard to thedouble bonds in the 5-membered ring.

(2) Preparation of (1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindene)dilithium salt

0.87 g (2.78 mmol) of (1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindene)was dissolved in 35 mL of ether and cooled to −78° C. To this solution,3.7 mL of a 1.57 mol/L solution of n-butyllithium in hexane(n-butyllithium: 5.81 mmol) was added dropwise over 30 minutes and thenthe mixture was warmed to room temperature and stirred for 8 hours.After distilling the solvent off under reduced pressure, the residue waswashed with hexane to obtain 1.03 g (2.58 mmol) of a dilithium salt asan ether adduct (yield: 92.8%).

This substance was subjected to ¹H-NMR analysis and the followingresults were obtained.

¹H-NMR (THF-d8) (δ, ppm): 2.20 (6H, s), 3.25 (8H, s), 6.0-7.4 (8H, m)

(3) Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

1.03 g (2.58 mmol) of an ether adduct of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindene) dilithium salt wassuspended in 25 mL of toluene and cooled to −78° C. To this, asuspension of 0.60 g (2.58 mmol) of zirconium tetrachloride in toluene(20 mL) was added over 20 minutes and the mixture was warmed to roomtemperature and stirred for 8 hours, and then the toluene supernatantwas filtered. The residue was extracted twice with 50 ml ofdichloromethane. The solvent was distilled off under reduced pressureand the residue was recrystallized from dichloromethane/hexane to obtain0.21 g (yield: 17.3%) of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride.

This substance was subjected to ¹H-NMR analysis and the followingresults were obtained.

¹H-NMR (CDCl₃):2.48 (6H, s), 3.33-3.85 (8H, m), 6.9-7 (8H, m)

[2] Polymerization

To a 10 L stainless steel autoclave, 5 L of heptane, 5 mmol oftriisobutylaluminium and a catalyst component, which had been obtainedby bringing 19 mmol as aluminum of a methyl aluminoxane (manufactured byAlbemarle) into preliminary contact with 19 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichlorideprepared in Step [1] described above in toluene for 30 minutes, werecharged and the mixture was heated to 40° C. and a propylene gas wasintroduced until the total pressure became 8.0 kg/cm²G. Duringpolymerization, the propylene gas was supplied using a pressurecontroller to keep a constant pressure, and after 1 hour the content wasrecovered and dried under reduced pressure to obtain polypropylene.

[3] Evaluation of Physical Characteristics

The physical characteristics were evaluated by the methods describedabove. The results are shown in Table I-1.

Example I-2

The procedure similar to that in Example I-1 was employed except forcharging 50 g of 1-butene (comonomer) additionally in Step [2] inExample I-1 and the physical characteristics were evaluated. The resultsare shown in Table I-1.

Example I-3 (1) Catalyst Preparation (1) Production of2-chlorodimethylsilylindene

Under nitrogen flow, a 1 L three-necked flask received 50 mL of THF(tetrahydrofuran) and 2.5 g (41 mmol) of magnesium and further received0.1 mL of 2-diburomoethane, and the mixture was stirred for 30 minutesto activate the magnesium. After stirring, the solvent was removed, and50 mL of THF was newly added. To the mixture, a solution of 5.0 g (25.6mmol) of 2-bromoindene in THF (200 mL) was added dropwise over 2 hours.After the addition was completed, the mixture was stirred at roomtemperature for 2 hours and then cooled to −78° C., and a solution of3.1 mL (25.6 mmol) of dichlorodimethylsilane in THF (100 mL) was addeddropwise over 1 hour and the mixture was stirred for 15 hours and thenthe solvent was distilled off. The residue was extracted with 200 mL ofhexane, and the solvent was distilled off to obtain 6.6 g (24.4 mmol) of2-clorodimethylsilylindene (yield: 94%).

(2) Preparation of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indene)

Under nitrogen flow, a 1 L three-necked flask received 400 mL of THF and8 g of 2-chlorodimethylsilylindene and the mixture was cooled to −78° C.To this solution, 38.5 mL (38.5 mmol) of a THF solution (1.0 M) ofLiN(SiMe₃)₂ was added dropwise. After stirring at room temperature for15 hours, the solvent was distilled off, and the residue was extractedwith 300 mL of hexane. The solvent was distilled off to obtain 2.2 g(6.4 mmol) of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indene)(yield: 33.4%).

(3) Preparation of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride

A Schlenk's bottle received 2.2 g (6.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indene) and 100 mL ofether and the mixture was cooled to −78° C. and combined with 9.6 mL(15.4 mmol) of n-butyllithium (solution in hexane: 1.6 M) and thenstirred at room temperature for 12 hours. The solvent was distilled offand the solid obtained was washed with 20 mL of hexane to obtain alithium salt (this lithium salt can be obtained quantitatively.). Thelithium salt thus obtained was dissolved in 100 mL of toluene and aseparate Schlenk's bottle received 1.5 g (6.4 mmol) of zirconiumtetrachloride and 100 mL of toluene. A 500 mL three-necked flaskreceived 100 mL of toluene, which was cooled to 0° C. and to which theequivalent amounts of the lithium salt obtained above and zirconiumtetrachloride were added dropwise using a cannula over 1 hours. Afterthe addition was completed, the mixture was stirred at room temperatureovernight. The solution was filtered and the solvent in the filtrate wasdistilled off. The solid obtained was recrystallized fromdichloromethane to obtain 1.2 g (2.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride (yield: 37%). This substance was subjected to ¹H-NMR analysisand the following results were obtained. ¹H-NMR (CDCl₃):0.85, 1.08 (6H,s), 7.11 (2H, s), 7.2-7.7 (8H, m)

[2] Polymerization

To a 10 L stainless steel autoclave, 5 L of heptane, 5 mmol oftriisobutylaluminium and a catalyst component, which had been obtainedby bringing 10 mmol as aluminum of a methyl aluminoxane (Albemarle) intopreliminary contact with 10 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride prepared in Step [1] described above in toluene for 5minutes, were charged and the mixture was heated to 50° C. and apropylene gas was introduced until the total pressure became 8.0kg/cm²G. During polymerization, the propylene gas was supplied using apressure controller to keep a constant pressure, and after 2.5 hours thecontent was recovered and dried under reduced pressure to obtainpolypropylene.

[3] Formulation and Kneading

The polypropylene thus obtained was combined with the followingadditives and extruded by a single-screw extruder (TSUKADAJUKISEISAKUSHO: Model TLC35-20) to granulate into a pellet.

Antioxidants

IRGANOX 1010, Ciba Specialty Chemicals: 1000 ppm;and,

IRGAPHOS 168, Ciba Specialty Chemicals: 1000 ppm [4] Evaluation ofPhysical Characteristics

The evaluation was made by the methods described above. The results areshown in Table I-1.

TABLE I-1 Example I-1 Example I-2 Example I-3 Resin analysis Intrinsicviscosity [η] (dl/g) 1.2 1.2 1.7 Molecular weight distribution 1.8 2.12.2 Mw/Mn % Isotactic pentad (mol %) 63.5 — 64.8 Boiling ether extract(wt/%) 5 8 5 TREF peak 63(s) 58(s) 67(s) TREF elution (W25) (wt %) 1.72.0 1.6 Comonomer content (mol %) — 0.9 — Stereoregularity (P) (mol %) —76 — Nucleating GELOL MD (ppm) — — — agent Resin Melting point Tm (° C.)102 98 111 characteristics Crystallization temperature (Tc) 63 56 72 (°C.) Press Tensile modulus (Mpa) 250 180 260 performance Izod impactstrength (kJ/m²) NB NB NB Transparency ∘ ∘ ∘ Internal haze 14 12 14 0.75× Tm − 15 61.5 58.5 68.3 (Note) TREF peak: (s); Sharp, (b); Broad N.B.:Not broken ∘∘: Excellent, ∘: Satisfactory, Δ: Poor

Example I-4 [1] Catalyst Preparation

(1,2′-dimethyl silylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride was obtained similarly as in Example 1-3.

[2] Polymerization

To a 10 L stainless steel autoclave, 6 L of heptane, 6 mmol oftriisobutylaluminium and a catalyst component, which had been obtainedby bringing 500 μmol as aluminum of a methyl aluminoxane (Albemarle)into preliminary contact with 5 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indenyl)zirconiumdichloride prepared in Step [1] described above in toluene for 5minutes, were charged and the mixture was heated to 50° C. and apropylene gas was introduced until the total pressure became 8.0kg/cm²G. During polymerization, the propylene gas was supplied using apressure controller to keep a constant pressure, and after 60 minutesthe content was recovered and dried under reduced pressure to obtainpolypropylene.

[3] Formulation and Kneading

The procedure employed in Example I-3 was followed.

[4] Evaluation of Physical Characteristics

The evaluation was made by the methods described above.

The results are shown in Table I-2.

Example I-5

The procedure similar to that in Example I-3 was employed except foradding GELOL MD (SHINIPPON RIKASHA). The results of the evaluation ofthe physical characteristics are shown in Table I-2.

Comparative Example I-1 [1] Catalyst Preparation (1) Preparation ofMagnesium Compound

A glass reactor (about 6 L in capacity) fitted with a stirrer was purgedsufficiently with a nitrogen gas and received about 2430 g of ethanol,16 g of iodine and 160 g of elemental magnesium, and the reaction wascontinued under pressure with stirring under reflux until the evolutionof a hydrogen gas from the reaction system was terminated to obtain asolid reaction product. The fluid reaction mixture containing this solidproduct was dried under reduced pressure to obtain a magnesium compound.

[2] Preparation of Solid Catalyst Component

A three-necked flask (capacity of 500 mL) purged sufficiently with anitrogen gas received 16 g of the magnesium compound obtained above (notpulverized), 80 mL of a purified heptane, 2.4 mL of silicontetrachloride and 2.3 mL of diethyl phthalate. The reaction system waskept at 90° C., and 77 mL of titanium tetrachloride was added withstirring and the reaction was continued at 110° C. for 2 hours and thenthe solid components were separated and washed with a purified heptaneat 80° C. Addition of 122 mL of titanium tetrachloride followed by thereaction at 110° C. for 2 hours followed by a sufficient washing with apurified heptane yielded a solid catalyst component.

[2] Polymerization

A 5 L stainless steel autoclave received 20 g of a polypropylene powder,2.5 mmol of triisobutylaluminium (TIBA), 0.125 mmol of1-allyl-3,4-dimethoxybenzene (ADMB), 0.2 mmol of dipheyldimethoxysilane(DPDMS) and 20 mL of a heptane solution containing 0.05 mmol as titaniumatom of the solid catalyst component obtained above, and the reactionsystem was vented for 5 minutes, and then a propylene gas was supplieduntil the total pressure became 28 kg/cm²G, whereby effecting a vaporphase polymerization for 1.7 hours to obtain a polymer.

[3] Evaluation f Physical Characteristics

Evaluation was made similarly as in Example I-1. The results are shownin Table I-2.

TABLE I-2 Comparative Example I-4 Example I-5 Example I-1 Resin analysisIntrinsic viscosity [η] (dl/g) 2.1 1.7 4.3 Molecular weight distribution2.3 2.2 4.7 Mw/Mn % Isotactic pentad (mol %) 65.0 64.8 65.3 Boilingether extract (wt/%) 4 5 12 TREF peak 67(s) 67(s) 113(b) TREF elution(W25) (wt %) 1.4 1.6 30 Comonomer content (mol %) — — — Stereoregularity(P) (mol %) — — — Nucleating GELOL MD (ppm) — 1000 — agent Resin Meltingpoint Tm (° C.) 111 112 161 characteristics Crystallization temperature71 80 100 (Tc) (° C.) Press Tensile modulus (Mpa) 264 278 480performance Izod impact strength (kJ/m²) NB NB NB Transparency ∘ ∘∘ ΔInternal haze 15 8 47 0.75 × Tm − 15 68.3 69.0 105.8 (Note) TREF peak:(s); Sharp, (b); Broad N.B.: Not broken ∘∘: Excellent, ∘: Satisfactory,Δ: Poor

Example I-6

The polypropylene obtained similarly as in Example I-1 was combined withthe following additives and extruded by a single-screw extruder(TSUKADAJUKISEISAKUSHO: Model TLC35-20) to granulate into a pellet.

Antioxidants

IRGANOX 1010, Ciba Specialty Chemicals: 1000 ppm;and,

IRGAPHOS 168, Ciba Specialty Chemicals: 1000 ppm

Neutralizing agent . . . Calcium stearate: 1000 ppmAnti-blocking agent . . . Silica-based agent: 2300 ppmSlipperiness-imparting (slipping) agent . . . Erucic acid amide: 2500ppm

Nucleating Agent

GELOL MD available from SHINNIPPON RIKASHA (dimethylbenzylidenesorbitol): 2300 ppm

The pellet obtained above was subjected to a film-forming processdescribed above and the film was qualified by the methods describedabove. The results are shown in Table I-3.

Example I-7

A propylene/butene copolymer obtained in a manner similar to that inExample I-2 was combined with the following additives and extruded by asingle-screw extruder (TSUKADA JUKISEISAKUSHO: Model TLC35-20) togranulate into a pellet.

Antioxidants

IRGANOX 1010, Ciba Specialty Chemicals: 1000 ppm;and,

IRGAPHOS 168, Ciba Specialty Chemicals: 1000 ppm

Neutralizing agent . . . Calcium stearate: 1000 ppmAnti-blocking agent . . . Silica-based agent: 2300 ppmSlipperiness-imparting (slipping) agent . . . Erucic acid amide: 2500ppm

Nucleating Agent

GELOL MD available from SHINNIPPON RIKASHA (dimethylbenzylidenesorbitol):2300 ppm

The pellet obtained above was subjected to a film-forming processdescribed above and the film was qualified by the methods describedabove. The results are shown in Table I-3.

Example I-8

A polypropylene obtained in a manner similar to that in Example I-1 wascombined with the following additives and extruded by a single-screwextruder (manufactured by TSUKADA JUKISEISAKUSHO: Model TLC35-20) togranulate into a pellet.

Antioxidants

IRGANOX 1010, Ciba Specialty Chemicals: 1000 ppm;and,

IRGAPHOS 168, Ciba Specialty Chemicals: 1000 ppm

Neutralizing agent . . . Calcium stearate: 1000 ppmAnti-blocking agent . . . Silica-based agent: 2300 ppmSlipperiness-imparting (slipping) agent . . . Erucic acid amide: 2500ppm

Nucleating Agent

GELOL MD available from SHINNIPPON RIKASHA (dimethylbenzylidenesorbitol): 500 ppm

The pellet obtained above was subjected to a film-forming processdescribed above and the film was qualified by the methods describedabove. The results are shown in Table I-3.

TABLE I-3 Example I-6 Example I-7 Example I-8 Resin analysis Intrinsicviscosity [η] (dl/g) 1.2 1.2 1.2 Molecular weight distribution 1.8 2.11.8 Mw/Mn % Isotactic pentad (mol %) 63.5 — 63.5 Boiling ether extract(wt/%) 5 8 5 TREF peak 63(s) 58(s) 63(s) TREF elution (W25) (wt %) 1.72.0 1.7 Comonomer content (mol %) — 0.9 — Stereoregularity (P) (mol %) —76 — Nucleating GELOL MD (ppm) 2300 2300 500 agent Resin Melting pointTm (° C.) 102 98 102 characteristics Crystallization temperature (Tc) 7874 78 (° C.) Film Tensile modulus (Mpa) 613 552 442 performance Impactresistance, 9900 9900 9900 Impact destruction strength (J/m) Haze 2.12.0 2.5 Heat seal temperature (° C.) 106 100 108 0.75 × Tm − 15 61.558.5 61.5 (Note) TREF peak: (s); Sharp, (b); Broad

Comparative Example I-2

The procedure similar to that employed in Example I-6 was followedexcept for adding no nucleating agent, but the film could not be formedbecause of an extremely poor roll release performance upon thefilm-forming process.

Comparative Example I-3

The procedure similar to that employed in Example I-6 was followedexcept for using a propylenic polymer E2900 available from IDEMITSUSEKYU KAGAKU which is produced using a non-metallocene catalyst(titanium/magnesium-based catalyst) and also except for adding nonucleating agent. The performance of the film thus obtained is shown inTable I-4.

Comparative Example I-4

The procedure similar to that employed in Example I-6 was followedexcept for using a propylenic polymer E2900 available from IDEMITSUSEKYU KAGAKU which is produced using a non-metallocene catalyst(titanium/magnesium-based catalyst). The performance of the film thusobtained is shown in Table I-4.

Comparative Example I-5 [1] Catalyst Preparation

Similarly as in Example I-1,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride.

[2] Polymerization

A 10 L stainless steel autoclave was charged sequentially with 5 L oftoluene, 20 mmol as aluminum of a methyl aluminoxane (Albemarle) andthen 20 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichlorideobtained in Example I-1, and heated to 50° C., and a propylene gas wasintroduced until the total pressure became 8.0 kg/cm²G. Duringpolymerization, the propylene gas was supplied using a pressurecontroller to keep a constant pressure, and after 1 hour the content wasrecovered and dried under reduced pressure to obtain polypropylene.

[3] Formulation and Kneading

The procedure employed in Example I-8 was followed.

[4] Evaluation of Physical Characteristics

The evaluation was made by the methods described above, but the filmcould not be formed because the film was broken during the film-formingprocess.

TABLE I-4 Comparative Comparative Comparative Example I-3 Example I-4Example I-5 Resin analysis Intrinsic viscosity [η] (dl/g) 1.9 1.9 0.7Molecular weight distribution 2.6 2.6 2.0 Mw/Mn % Isotactic pentad (mol%) 72.2 72.2 59.2 Boiling ether extract (wt/%) 12 12 6 TREF peak 112(b)112(b) 58(s) TREF elution (W25) (wt %) 30 30 1.5 Comonomer content (mol%) — — — Stereoregularity (P) (mol %) — — — Nucleating GELOL MD (ppm) —2300 500 agent Resin Melting point Tm (° C.) 160 160 — characteristicsCrystallization temperature 102 103 — (Tc) (° C.) Film Tensile modulus(Mpa) 512 514 — performance Impact resistance, 9800 9800 — Impactdestruction strength (J/m) Haze 15.5 15.8 — Heat seal temperature (° C.)151 151 — 0.75 × Tm −15 105 105 — (Note) TREF peak: (s); Sharp, (b);Broad

[Second Invention]

A method for evaluating the resin characteristics and the physicalcharacteristics of a polymer according to the invention are describedbelow.

(1) Intrinsic Viscosity [η]

An automatic viscometer model VMR-053 available from RIGOSHA (KK) wasused in a tetralin solvent at 135° C.

(2) % Pentad and % Abnormal Insertion

Measurement was made in accordance with the method described in thedetailed description of the invention. Thus, a % meso-pentad (% mmmm)and a % racemi-pentad (% rrrr) referred herein were obtained inaccordance with the method proposed by A. Zambelli et al inMacromolecules, 6, 925 (1973) by determining the methyl signal in a¹³C-NMR spectrum and calculating % meso and % racemi levels, in apolypropylene molecule chain, as represented in pentad as a unit. Thecalculation was made in accordance with the method described in thedetailed description of the invention.

With regard to (m−2, 1), (r−2, 1) and (1,3), the peaks in a ¹³C-NMRspectrum were assigned in accordance with the report by Grassi et al(Macromolecules, 21., p. 617 (1988)) and the report by Busico et al(Macromolecules, 27, p. 7538 (1994)) and each % insertion content wascalculated based on the integrated intensity of each peak. A value(m−2, 1) was obtained by calculating the ratio of the integratedintensity of a peak assigned to Pα,γ threo observed near 17.2 ppm to theintegrated intensity in all methyl carbon region as a % meso-2,1insertion content. A value (r−2, 1) was obtained by calculating theratio of the integrated intensity of a peak assigned to Pα,γ threoobserved near 15.0 ppm to the integrated intensity in all methyl carbonregion as a % rasemi-2,1 insertion content. A value (1, 3) was obtainedby calculating the ratio of the integrated intensity of a peak assignedto Tβ,γ+ observed near 31.0 ppm to the integrated intensity in allmethine carbon region as a % 1,3 insertion content. When a peak to beassigned to a meso-2, 1 insertion, a racemi-2, 1 insertion or a 1, 3insertion could not be distinguished because of, for example, beingoverlapped with noises, then each heterogeneous binding content (m−2,1), (r−2, 1) or (1, 3) was regarded as a zero value.

A ¹³C NMR spectrum was obtained using the following instruments underthe conditions specified below.

Instrument: Nippon Densi Model JNM-EX400 ¹³C-NMR deviceMethod: Proton complete decoupling methodConcentration: 220 mg/milliliterSolvent: A 90/10 solvent mixture (by volume) of 1,2,4-Trichlorobenzeneand benzene-d6

Temperature: 130° C. Pulse gap: 450

Pulse interval: 4 secondsNumber of cycles: 10000 times

(3) Comonomer Unit Content (% by Mole) in Copolymer

A ¹³C NMR spectrum was obtained using Nippon Densi Model JNM-EX400¹³C-NMR device under the conditions specified below and the calculationwas made as described below.

Sample concentration: 220 mg/3 ml NMR solventNMR Solvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10 v/v)Determination temperature: 130° C.

Pulse gap: 450

Pulse interval: 10 secondsNumber of cycles: 4000 times

(a) Ethylene Unit

A random copolymer of propylene and ethylene, when subjected to ¹³C-NMR,exhibited the spectrum whose signals had the chemical shifts and theassignments indicated in Table II-1.

TABLE II-1 Assignments of signals in ¹³C-NMR spectrum ofethylene-propylene copolymer Chemical Number shift Assignment 145.1-47.3 PPP Sαα 2 42.3 PPP Sαα 3 38.6 PPP Tαγ 4 38.0 Sαγ 5 37.5 Sαδ 636.0 PPP Sαβ 7 36.0 PPP Tαβ 8 34.9 EPP, PEP Sαβ 9 34.6 EPP, PEP Sαβ 1034.1 EPP Tγγ 11 33.7 EEPP Tγδ 12 33.3 EPE Tδδ 13 31.6 PPP Tβγ 14 31.4EPP Tβγ 15 31.0 PPE Tβδ 16 30.7 PPP Sαβ 17 30.5 PEEE Sγδ 18 30.0 EEE Sδδ19 29.0 PPP Tββ 20 27.3 PEE Sβδ 21 24.6 PEP Sαβ 22 21.3-22.7 Pββ 2320.6-21.3 Pββ 24 19.8-20.6 Pββ 25 17.6 Pαβ 26 17.2 Pαγ (NOTE) Erepresents an ethylene unit. A chemical shift is represented in ppm.

The ethylene unit content in the copolymer (a (% by mole)) was obtainedin accordance with the following equation (1) based on the spectrumdetermined by the ¹³C-NMR.

α=E/S×100  (1)

wherein S and E are each represented as follows:

S=IEPE+IPPE+IEEE+IPPP+IPEE−IPEP

E=IEEE+2/3(IPEE+IEPE)+1/3(IPPE+IPEP)

wherein:

IEPE=I(12)

IPPE=I(15)+I(11)+(I(14)−I(11))/2+I(10)

IEEE=I(18)/2+I(17)/4

IPPP=I(19)+(I(6)+I(7))/2+I(3)+I(13)+I(11)+(I(14)−I(11))/2

IPEE=I(20)

IPEP=(I(8)+I(9)−2×(I(11))/4+I(21).

A % isotactic triad of a PPP chain was obtained as a stereoregularityindex (P (% by mole)) according to the equation (2) shown below.

P=Im/I×100  (2)

wherein Im and I are each represented as follows:

Im=1  (22)

I=I(22)+I(23)+I(24)−{(I(8)+I(9))/2+I(10)+3/2×I(11)+I(12)+I(13)+I(15)}.

In the equation shown above, I(1), I(2) and the like represent theintensities of signal [1], signal [2] and the like, respectively.

(4) Molecular Weight Distribution (Mw/Mn)

Measurement was made in accordance with the method described in thedetailed description of the invention.

(5) DSC Analysis

Analysis was made in accordance with the method described in thedetailed description of the invention.

(6) Temperature-Raising Fractional Chromatography

Measurement was made by the method described in the first invention.

(7) Tensile Modulus

Measurement was made by the method described in the first invention.

(8) Internal Haze

A propylenic polymer was press-molded to obtain a test piece which wassubjected to the test in accordance with JIS K7105.

Test piece: 15 cm×15 cm×1 mm (test piece thickness=1 mm)

(9) % Elasticity Recovery

The method described in JP-A-5-132590 was followed. Thus, a propylenicpolymer was press-molded and a JIS No. 2 dumb-bell test specimen wasprepared. The constant-width region of the dumb-bell was marked at 25 mminterval, which was designated as L0. The specimen was stretched using atensile test device from 80 mm to 160 mm of the inter-chuck distance atthe stretching speed of 50 mm/min, and then the inter-chuck distance wasallowed to become the initial length, and then after one minute thedistance between the marks was determined and designated as L1. A %elasticity recovery was calculated by the equation shown below. When thevalue obtained was zero then the result was judged as “No recovery”.

[(2L0−L1)/L0]×100

L0: Initial distance between marks on dumb-bell

L1: Distance between marks on dumb-bell after stretching

(10) Anti-Blocking Ability

A propylenic polymer was press-molded to obtain a test piece, which wasbound in the conditions described below and examined for its peelingstrength by a tensile test device.

Test piece: 15 cm×62.5 mm×2 mm

-   -   Binding conditions: Bound at 40° C. over the area of 15 mm×31 mm        under the pressing load of 0.7 kg for 3 hours.

Shear peeling conditions: Crosshead speed of 50 mm/min

(11) Izod Impact Strength

A propylenic polymer was press-molded to obtain a test piece which wassubjected to the test in accordance with JIS K-7110 with the test piecethickness of 3 mm at the ambient temperature of −5° C.

(12) Amount of Components Dissolved Out into Hexane (H25)

A value of H 25 was determined under the conditions specified below.

Sample size: 0.1 to 5 gState of sample: Powder (a pellet should be pulverized into a powderbefore use)

Solvent: Hexane

Elution conditions: Allowing to stand at 25° C. for 3 days or longerCalculation of amount eluted: According to the following equation:

H25=[(W0−W1)/W0]×100(%)

(13) Boiling Diethylether Extract

The method similar to that in the first invention was employed exceptthat the sample size was 1 to 2 g.

Example II-1 Propylene Homopolymer (1) Catalyst Preparation Synthesis of(Dimethylsilylene) 2 (3-n-butylindenyl)2 zirconium dichloride

A Schlenk's bottle receives 0.83 g (2.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indene)2 and 50 mL ofether. The mixture is cooled to −78° C. and combined with 3.1 mL (5.0mmol) of n-BuLi (1.6 M solution in hexane) and then stirred at roomtemperature for 12 hours. The solvent is distilled off to obtain a solidwhich is washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of alithium salt as an ether adduct. This lithium salt is dissolved in 50 mLof THF, and cooled to −78° C., 0.57 mL (5.3 mmol) of n-butyl bromide isadded dropwise slowly and the mixture is stirred at room temperature for12 hours. After distilling the solvent off followed by extraction with50 ml of hexane followed by removing the solvent, 0.81 g (1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindene)2 wasobtained (yield: 74%).

0.81 g (1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindene)₂ thusobtained is placed in a Schlenk's bottle under nitrogen flow togetherwith 100 mL of ether. The mixture is cooled to −78° C. and combined with2.7 mL (4.15 mmol) of n-BuLi (1.54 M solution in hexane) and thenstirred at room temperature for 12 hours. The solvent was distilled offto obtain a solid which is washed with hexane to obtain 0.28 g (1.43mmol) of a lithium salt as an ether adduct.

The lithium salt thus obtained is dissolved in 50 mL of toluene undernitrogen flow. The mixture is cooled to −78° C. and treated dropwisewith 0.33 g (1.42 mmol) of zirconium tetrachloride suspended in toluene(50 mL) which has previously been cooled to −78° C. After the dropwisetreatment, the mixture is stirred at room temperature for 6 hours. Afterfiltration, the solvent of the filtrate is distilled off.Recrystallization from dichloromethane yielded 0.2 g (0.32 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindenyl)₂zirconium dichloride (yield: 22%).

The results of ¹H-NMR (90 MHz, CDCl₃) analysis are as follows: δ 0.88,0.99 (12H, dimethylsilylene), 0.7-1.0. 1.1-1.5 (18H, n-Bu), 7.0-7.6 (8H,benzene ring proton).

(2) Propylene Polymerization

A 10 L stainless steel autoclave received 6 L of heptane, 6 mmol oftriisobutylaluminium and a catalyst component which had been obtained bybringing 5 mmol of a methyl aluminoxane (manufactured by Albemarle) intopreliminary contact with 5 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindenyl) 2zirconium dichloride in toluene for 5 minutes. After introducinghydrogen at 0.5 kg/cm²G, a propylene gas was introduced until the totalpressure became 8.0 kg/cm²G, and the propylene gas was supplied using apressure controller to keep a constant pressure during polymerization.After polymerizing at 50° C. for 30 minutes, the content was recoveredand dried under reduced pressure to obtain a propylene homopolymer.

(3) Formulation and Kneading

The polypropylene homopolymer thus obtained was combined with thefollowing additives and extruded by a single-screw extruder(manufactured by TSUKADA JUKISEISAKUSHO: Model TLC35-20) to granulateinto a pellet.

(Formulation of Additives) Antioxidants

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppm

Phosphorus-based antioxidant: P-EPQ 500 ppm

Neutralizing agent: Calcium stearate: 500 ppm

Neutralizing agent: DHT-4A: 500 ppm

(4) Evaluation of Resin Characteristics and Physical Characteristics

Evaluation was made by the methods described above. The results areshown in Table II-2 and Table II-3. In these tables, Example 1 meansExample II-1. The same applies analogously to Example 2 or later as wellas Comparatives. The description further thereafter is also handledsimilarly.

Example II-2 Propylene Homopolymer

The method similar to that in Example II-1 was employed except forproducing a propylene homopolymer without hydrogenation. The results areshown in Tables II-2 and 11-3.

Example II-3 (1) Synthesis of (dimethylsilylene)2 (3-methylindenyl)2zirconium dichloride

A Schlenk's bottle receives 2.2 g (6.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indene) and 100 mL ofether. The mixture is cooled to −78° C. and combined with 9.6 mL (15.4mmol) of n-BuLi (1.6 M solution in hexane) and then stirred at roomtemperature for 12 hours. The solvent is distilled off to obtain a solidwhich is washed with 20 ml of hexane to obtain a lithium saltquantitatively. This lithium salt is dissolved in 100 mL of THF andcooled to −78° C. 7.4 g (52.0 mmol) of methyl iodide was added dropwiseslowly and the mixture is stirred at room temperature for 12 hours.After distilling the solvent off followed by extraction with 50 ml ofhexane followed by removing the solvent off, 4.5 g (12 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindene) 2 wasobtained (yield: 94%).

Subsequently, a Schlenk's bottle receives under nitrogen flow 2.0 g (5.4mmol) of (1.2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindene)2and 100 mL of ether. The mixture is cooled to −78° C. and combined with13.5 mL (21.6 mmol) of n-BuLi (1.6 M solution in hexane) and thenstirred at room temperature for 12 hours. The solvent is distilled offto obtain a solid which is washed with hexane to obtain 1.1 g (2.9 mmol)of a lithium salt. Under nitrogen flow, the lithium salt obtained aboveis dissolved in 100 mL of toluene. The mixture is cooled to −78° C., andtreated dropwise with 0.7 g (3.0 mmol) of zirconium tetrachloridesuspended in toluene (100 ml) which has previously been cooled to −78°C. After completion of the addition, the mixture is stirred for 6 hoursat room temperature. After filtration, the precipitate was extractedwith dichloromethane. Recrystallization from dichloromethane/hexaneyielded 0.5 g (0.94 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindenyl) 2zirconium dichloride (yield: 32%).

The results of ¹H-NMR (CDCl₃) analysis are as follows: δ 0.95, 1.05(12H, dimethylsilylene), 2.50 (6H, CH3), 7.2-7.7 (8H, Ar—H).

(2) Propylene Polymerization

A 1 L stainless steel autoclave received 400 mL of heptane, 0.5 mmol oftriisobutylaluminium and a catalyst component which had been obtained bybringing 0.5 mmol of a methyl aluminoxane (manufactured by Albemarle)into preliminary contact with 0.5 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindenyl) 2zirconium dichloride in toluene for 5 minutes. After introducinghydrogen at 0.3 kg/cm²G, a propylene gas was introduced until the totalpressure became 8.0 kg/cm²G, and the propylene gas was supplied using apressure controller to keep a constant pressure during polymerization.After polymerizing at 70° C. for 1 hour, the content was recovered anddried under reduced pressure to obtain a propylene homopolymer.

(3) Formulation and Kneading

Except for combining the polypropylene homopolymer thus obtained withthe following additives shown below, the procedure similar to that inExample II-1 was employed.

(Formulation of Additives)

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppm

Phosphorus-based antioxidant: IRGAPHOS168 available from Ciba SpecialtyChemicals: 1000 ppm

(4) Evaluation of Resin Characteristics and Physical Characteristics

Evaluation was made similarly as in Example II-1 (4). The results areshown in Tables II-2 and II-3.

Example II-4 Propylenic Copolymer (1) Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

The method similar to that described in Example I-1 was employed.

(2) Propylene/Ethylene Copolymerization

A 2 L stainless steel autoclave received 1.2 L of toluene, 1.5 mmol oftriisobutylaluminium, 10 (Al) mmol of a methyl aluminoxane (Albemarle)and 20 μmol of(1,2′-ethylene)(2,1′-ethylene)bis(3-methylindenyl)zirconium dichlorideand the mixture was warmed to 30° C., and then an ethylene/propylene gasmixture (molar ratio of ethylene/propylene=1/100) was introduced. Anexcessive gas was vented so that the total pressure became 7.0 kg/cm²G,and the polymerization was effected for 60 minutes while keeping aconstant gas composition in the reaction system, and then the contentwas recovered and dried under reduced pressure to obtain a propyleniccopolymer. The formulation and the kneading, and the evaluation of theresin characteristics and the physical characteristics were performed inthe manner similar to that in Example II-1. The results are shown inTables II-1 and II-3.

Comparative Example II-1 Propylene Homopolymer (1) Preparation ofMagnesium Compound

The method similar to that in Comparative I-1 was employed.

(2) Preparation of Solid Catalyst Component (A)

A glass reactor whose capacity was 5 L and which has sufficiently beenpurged with a nitrogen gas was charged with 160 g of the magnesiumcompound obtained in Step (1) described above (not pulverized), 800 mlof a purified heptane, 24 ml of silicon tetrachloride and 23 ml ofdiethyl phthalate and then the reaction system was kept at 80° C. andadmixed with 770 ml of titanium tetrachloride with stirring, and thereaction was continued at 110° C. for 2 hours and then the solidcomponents were separated and washed with a purified heptane at 90° C.1220 ml of titanium tetrachloride was further added, and the reaction at110° C. for 2 hours followed by a thorough washing with a purifiedheptane yielded a solid catalyst component (A).

(3) Vapor Phase Polymerization of Propylene

A polymerization chamber whose capacity was 200 L was fed with 6.0 g/hof the solid catalyst component obtained in Step (2) described above,0.2 mol/h of triisobutylaluminium (TIBA), 0.012 mol/h of1-allyl-3,4-dimethoxybenzene (ADMB), 0.012 mol/h ofcyclohexylmethyldimethoxysilane (CHMDMS) and 37 kg/h of propylene, andthe polymerization was effected at 70° C. under 28 kg/cm²G.

(4) Formulation and Kneading

The polypropylene powder thus obtained was admixed with2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane and then combined with theadditives as described in Example II-1 and extruded via a 40 mmφ die toobtain a pellet.

(5) Evaluation of Resin Characteristics and Physical Characteristics

The method similar to that in Example II-1 (4) was employed. The resultsare shown in Tables II-2 and 11-3.

Reference Example Affinity PL1880

The pellet of Affinity PL1880 (trade name) available from Dow ChemicalJapan (K.K.9 was subjected to the evaluation of the physicalcharacteristics as described in Example II-1 (4). The results are shownin Table II-3.

Comparative Example II-2 Propylene Homopolymer

A stainless steel autoclave whose capacity was 1 L was charged with 400mL of heptane, 0.5 mmol of triisobutylaluminium and a catalyst componentwhich had been obtained by bringing 2 μmol of dimethylanilinium(pentafluorophenyl)borate into preliminary contact with 1 μmol of(t-butylamide) dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane titaniumdichloride in toluene for 5 minutes. After introducing hydrogen at 0.3kg/cm²G, a propylene gas was introduced until the total pressure became8.0 kg/cm²G, and the propylene gas was supplied using a pressurecontroller to keep a constant pressure during polymerization. Afterpolymerizing at 70° C. for 1 hour, the content was recovered and driedunder reduced pressure to obtain a propylene homopolymer. Theformulation and the kneading, and the evaluation of the resincharacteristics and the physical characteristics were performed in themanner similar to that in Example II-i. The results are shown in TablesII-2 and 11-3.

Example II-5 Addition of Nucleating Agent

Except for combining the propylene homopolymer obtained in Example II-1with the following additives shown below, the procedure similar to thatin Example II-1 was employed. The results are shown in Table II-4.

(Formulation of Additives)

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppm

Phosphorus-based antioxidant: P-EPQ, 500 ppm

Neutralizing agent: Calcium stearate: 500 ppm

Neutralizing agent: DHT-4A: 500 ppm

Nucleating agent: GELOL MD available from SHINNIPPON RIKAGAKUSHA: 1000ppm

Example II-6 Addition of Nucleating Agent

Except that the amount of GELOL MD available from SHINNIPPON RIKAGAKUSHAwhich was added was 2000 ppm, the method similar to that in Example II-5was employed. The results are shown in Table II-4.

Example II-7 Addition of Nucleating Agent

Except for combining the propylene homopolymer obtained in Example II-1with the following additives shown below, the procedure similar to thatin Example II-1 was employed. The results are shown in Table II-4.

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppm

Phosphorus-based antioxidant: IRGAPHOS 168 available from Ciba SpecialtyChemicals: 1000 ppm

Nucleating agent: GELOL MD available from SHINNIPPON RIKAGAKUSHA: 5000ppm

Example II-8 Addition of Nucleating Agent

Except that the amount of GELOL MD available from SHINNIPPON RIKAGAKUSHAwhich was added was 10000 ppm, the method similar to that in ExampleII-7 was employed. The results are shown in Table II-4.

Example II-9 Addition of Nucleating Agent

Except for employing 2000 ppm of NA-11 available from DENKASHA insteadof 5000 ppm of GELOL MD available from SHINNIPPON RIKAGAKUSHA, themethod similar to that in Example II-7 was employed. The results areshown in Table II-4.

Example II-10 Effect of Modifier

Polypropylene E105 GM manufactured by IDEMITSU SEKIYU KAGAKU wascombined with the pellet obtained in Example II-1 and extruded by asingle-screw extruder (manufactured by TSUKADA JUKISEISAKUSHO: ModelTLC35-20) to granulate into a pellet. The physical characteristics wereevaluated similarly as in Example II-1 (4). The results are shown inTable II-5.

Example II-11 Effect of Modifier

Except for changing the ratio of the pellet obtained in Example II-1into 60% by weight, the procedure similar to that in Example II-10 wasemployed. The results are shown in Table II-5.

Example II-12 Effect of Modifier

Except for changing the ratio of the pellet obtained in Example II-1into 30% by weight, the procedure similar to that in Example II-10 wasemployed. The results are shown in Table II-5.

Comparative Example II-3

Polypropylene E105 GM manufactured by IDEMITSU SEKIYU KAGAKU wassubjected to the evaluation of the physical characteristics similarly asin Example II-1 (4). The results are shown in Table II-5.

Comparative Example II-4

Except for combining 50% by weight of the polymer obtained inComparative II-2 with Polypropylene E105 GM manufactured by IDEMITSUSEKIYU KAGAKU, the procedure similar to that in Example II-10 wasemployed. The results are shown in Table II-5.

TABLE II-2 Comparative Comparative Item Example 1 Example 2 Example 3Example 4 Example 1 Example 2 Comonomer content, % by — — — 10 — — moleW25, % by weight 93 90 80 56 30 99 H25, % by weight 17 15 15 42 6 100 Tm° C. nd nd 70 76 159 nd ΔH J/mol nd nd 7 19 61 nd 6 × (Tm−140) nd nd−420 −384 111.6 nd % mmmm, % by mole 41 41 46 — 65 2 P, % by mole — — —76 — — rrrr/(1 − mmmm) 0.04 0.04 0.04 — 0.23 0.11 Mw/Mn 2.4 2.0 2.5 6.12.7 2.2 [η] dl/g 2.5 4.4 2.5 0.7 2.1 1.9 % 2, 1 insertion, % by mole 0 00 — 0 4.4 % 1, 3 insertion, % by mole 0 0 0 — 0 0 Boiling diethyletherextract 30 29 25 56 12 63 % by weight Tc ° C. nd nd nd 18 104 nd (NOTE)n.d: Not detected,

Example 1 means Example II-1. The same applies analogously hereinafter.

TABLE II-3 Comparative Comparative Reference Item Example 1 Example 2Example 3 Example 4 Example 1 Example 2 Example Tensile modulus Mpa 3134 52 60 330 2 85 Internal haze % 4 3 4 10 60 4 10 % Elasticity 69 78 3328 No recovery 79 No recovery % recovery Anti-blocking ability 5 5 4 6 0No peeling 3 kg/cm² Izod impact strength 2.8 3.4 2.5 5.0 2.1 4.3 Nobreak KJ/m² (Note) Izod impact strength: Determined at −5° C. withnotches being formed

TABLE II-4 Exam- Exam- Exam- Exam- Exam- Exam- Item ple 1 ple 5 ple 6ple 7 ple 8 ple 9 Nucleating — GELOL GELOL GELOL GELOL NA-11 agent MD MDMD MD Nucleating — 1000 2000 5000 10000 2000 agent level ppm Tm ° C. ndnd 64 65 64 64 Tc ° C. nd nd nd nd nd nd Tensile 30 32 35 41 42 32modulus Mpa Internal haze % 4 5 5 5 4 5 % Elasticity 69 70 72 75 76 76recovery % Izod impact 2.8 3.2 2.9 5.0 2.9 7.1 strength KJ/m² (NOTE)Izod impact strength: Determined at −5° C. with notches being formed

TABLE II-5 Example Example Example Comparative Comparative ComparativeItem 10 11 12 Example 1 Example 3 Example 4 Tensile modulus 190 230 560330 1500 240 Mpa Internal haze % 33 43 54 60 44 71 % Elasticity 20 1 NoNo recovery No recovery No recovery recovery % recovery Izod impactstrength 2.5 2.4 1.9 2.1 1.9 1.6 KJ/m² (NOTE) Izod impact strength:Determined at −5° C. with notches being formed

[Third Invention]

A method for evaluating the resin characteristics and the physicalcharacteristics of a polymer according to the invention are describedbelow.

(1) Intrinsic Viscosity [η]

Measurement was made by the method described in the first invention.

(2) % Pentad and % Abnormal Insertion

Measurement was made by the method described in the second invention.

(3) Comonomer Unit Content (% by mole) in Copolymer

Measurement was made by the method described in the second invention.

(4) Molecular Weight Distribution (Mw/Mn)

Measurement was made by the method described in the first invention.

(5) DSC Analysis

Measurement was made by the method described in the second invention.

(6) Temperature-Raising Fractional Chromatography

Measurement was made by the method described in the first invention.

(7) Amount of Components Dissolved out into Hexane (H25)

Measurement was made by the method described in the second invention.

(8) Boiling Diethylether Extract

Measurement was made by the method described in the first invention.

(9) Frequency Distribution Determination of Melt Viscoelasticity

A value of (η*) (Pa·s) is obtained using a rotary rheometer (ARES)manufactured by RHEOMETRIX together with a parallel plate (25 mm indiameter, imm in gap) at the temperature of 230° C. and at the initialstrain of 20% or less.

(10) Tensile Modulus

Measurement was made by the method described in the second invention.

Example III-1 Propylene Homopolymer (1) Catalyst Preparation(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butylindenyl)zirconiumdichloride

A Schlenk's bottle receives 0.83 g (2.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(indene) and 50 mL ofether. The mixture is cooled to −78° C. and combined with 3.1 mL (5.0mmol) of n-BuLi (1.6 M solution in hexane) and then stirred at roomtemperature for 12 hours. The solvent is distilled off to obtain a solidwhich is washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of alithium salt as an ether adduct. This lithium salt is dissolved in 50 mLof THF and cooled to −78° C. 0.57 mL (5.3 mmol) of n-butyl bromide isadded dropwise slowly and the mixture is stirred at room temperature for12 hours. After distilling the solvent off followed by extraction with50 mL of hexane, followed by removing the solvent, 0.81 g (1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butylindene)(yield: 74%).

Subsequently, 0.81 g (1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butylindene)obtained above and 100 mL of ether are placed in a Schlenk's bottleunder nitrogen flow. The mixture is cooled to −78° C. and combined with2.7 mL (4.15 mmol) of n-BuLi (1.54M solution in hexane) and then stirredat room temperature for 12 hours. The solvent is distilled off to obtaina solid which is washed with hexane to obtain 0.28 g (1.43 mmol) of alithium salt as an ether adduct.

Under nitrogen flow, the lithium salt obtained above is dissolved in 50mL of toluene. The mixture is cooled to −78° C. and treated dropwisewith 0.33 g (1.42 mmol) of zirconium tetrachloride suspended in toluene(50 mL) which has previously been cooled to −78° C. After dropwisetreatment, the mixture is stirred at room temperature for 6 hours.Subsequently the mixture is filtered and the solvent of the filtrate isdistilled off. Recrystallization from dichloromethane yielded 0.2 g(0.32 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butyl) zirconiumdichloride (yield 22%).

The results of ¹H-NMR (90 MHz, CDCl₃) analysis are as follows: δ 0.88,0.99 (12H, dimethylsilylene), 0.7-1.0.

1.1-1.5 (18H, n-Bu), 7.0-7.6 (8H, benzene ring proton).

(2) Propylene Homopolymerization

A 1 L stainless steel, pressure-resistant autoclave fitted with astirrer was heated to 80° C. and dried under reduced pressurethoroughly, and then it was allowed to be at atmospheric pressure with adry nitrogen and allowed to cool to room temperature. Under dry nitrogenflow, 400 mL of dried deoxygenated heptane and 0.5 mL (1.0 mmol) of asolution of triisobutylaluminium (2.0 M) in heptane were added andstirred at 350 rpm for a while. On the other hand, a thoroughlynitrogen-purged 50 mL Schlenk's bottle were charged under nitrogen flowwith toluene (10 mL) and a solution of triisobutylaluminium in heptane(2M, 0.5 mL, 1.0 mmol) and then with a solution of a methyl aluminoxanein toluene (1.43 M, 0.35 mL, 0.5 mmol) and a slurry of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-n-butylindenyl)zirconiumdichloride obtained in Step (1) described above in heptane (5 mol/mL,0.1 mL, 0.5 mol), which were stirred at room temperature for 5 minutes.The catalyst slurry was placed rapidly in the autoclave.

(First Step Polymerization)

Subsequently, the stirring was initiated at 400 rpm, and the propylenepressure was raised slowly to 8.0 kg/cm² as a total pressure, and at thesame time the temperature was raised slowly to 70° C. The polymerizationwas effected for 20 minutes.

(Second Step Polymerization)

Subsequently, the temperature was lowered to 30° C. over a period of 5minutes, and after the completion of additional 35-minutepolymerization, unreacted propylene was removed by depressurization. Thereaction mixture was poured into 2 L of methanol to precipitatepolypropylene, which was filtered and dried to obtain 17 g ofpolypropylene. The resin characteristics and the physicalcharacteristics described above were determined and the results areshown in Table III-1.

In this table, Example 1 means Example III-1. The same appliesanalogously to Example 2 or later as well as Comparatives.

Example III-2 Propylene Homopolymerization (Hydrogenation Upon SecondStep Polymerization) (Catalyst Preparation)

The method similar to that in Example III-1 was employed.

(First Step Polymerization)

Subsequently, the stirring was initiated at 400 rpm, and the propylenepressure was raised slowly to 8.0 kg/cm²G as a total pressure, and atthe same time the temperature was raised slowly to 50° C. Thepolymerization was effected for minutes.

(Second Step Polymerization)

Subsequently, unreacted propylene was depressurized to 1.0 kg/cm²G.Hydrogen was then introduced at the pressure of 0.3 kg/cm²G. Thepropylene pressure was then raised slowly to 8.0 kg/cm²G as a totalpressure, and the temperature was raised slowly to 70° C., and thepolymerization was effected for minutes. After completion of thereaction, unreacted propylene was removed by depressurization. Thereaction mixture was poured into 2 L of methanol to precipitatepolypropylene, which was filtered and dried to obtain 32 g ofpolypropylene. The resin characteristics and the physicalcharacteristics described above were determined and the results areshown in Table III-1.

Example III-3 Propylenic Copolymer (1) Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

The method similar to that in Example I-1 in the first invention wasemployed.

(2) Propylene/Ethylene Copolymerization

A 2 L stainless steel autoclave received 1.2 L of toluene, 1.5 mmol oftriisobutylaluminium, 10 (Al) mmol of a methyl aluminoxane (Albemarle)and 20 μmol of(1,2′-ethylene)(2,1′-ethylene)bis(3-methylindenyl)zirconium dichlorideand the mixture was warmed to 30° C., and then an ethylene/propylene gasmixture (molar ratio of ethylene/propylene=1/100) was introduced. Anexcessive gas was vented so that the total pressure became 7.0 kg/cm²G,and the polymerization was effected for 60 minutes while keeping aconstant gas composition in the reaction system, and then the contentwas recovered and dried under reduced pressure to obtain a propyleniccopolymer. The evaluation of the resin characteristics and the physicalcharacteristics described above were examined and the results are shownin Table III-1.

Comparative III-1 Single Step Polymerization of Propylene(Hydrogenation) (Catalyst Preparation)

The method similar to that in Example III-1 was employed.

(Polymerization)

Subsequently, hydrogen was introduced until the pressure became 1.0kg/cm²G, and the stirring was initiated at 400 rpm. Then the propylenepressure was raised slowly to 8.0 kg/cm²G as a total pressure, and atthe same time the temperature was raised slowly to 50° C., and thepolymerization was effected for 60 minutes. After completion of thereaction, unreacted propylene was removed by depressurization. Thereaction mixture was poured into 2 L of methanol to precipitatepolypropylene, which was filtered and dried to obtain 38 g ofpolypropylene. The resin characteristics and the physicalcharacteristics described above were determined and the results areshown in Table III-1.

Comparative III-2 Propylene Homopolymer (Non-Hydrogenation) (CatalystPreparation)

The method similar to that in Example III-1 was employed.

(Polymerization)

Subsequently, the stirring was initiated at 400 rpm. Then the propylenepressure was raised slowly to 8.0 kg/cm² G as a total pressure, and atthe same time the temperature was raised slowly to 30° C., and thepolymerization was effected for 60 minutes. After completion of thereaction, unreacted propylene was removed by depressurization. Thereaction mixture was poured into 2 L of methanol to precipitatepolypropylene, which was filtered and dried to obtain 13 g ofpolypropylene. The resin characteristics and the physicalcharacteristics described above were determined and the results areshown in Table III-1.

TABLE III-1 Comparative Comparative Item Example 1 Example 2 Example 3Example 1 Example 2 Resin Comonomer content, % by — — 10 — —characteristics/ mole physical H25, % by weight 15 117 42 117 115characteristics Tm ° C. nd nd 76 nd nd ΔH J/mol nd nd 19 nd nd 6 ×(Tm−140) — — −384 — — % mmmm, % by mole 40 41 — 41 42 P, % by mole — —76 — — rrrr/(1 − mmmm) 0.04 0.04 — 0.04 0.04 Mw/Mn 9.6 4.5 6.1 2.1 2.2[η] dl/g 10.3 2.8 0.7 3.0 13.7 W25, % by weight 94 93 56 93 94 η* Pa · s1590 920 840 1230 2930 159η + 743 2381 1185 854 1218 2921 % 2, 1insertion, % by mole 0 0 0 0 4.4 % 1, 3 insertion, % by mole 0 0 0 0 0Boiling diethylether 25 30 56 31 23 extract, % by weight Tc ° C. nd ndnd nd nd Tensile modulus MPa 37 30 60 26 47 (NOTE) nd: Not detected

[Fourth Invention]

A method for evaluating the resin characteristics and the physicalcharacteristics of a polymer according to the invention are describedbelow.

(1) Intrinsic Viscosity [η]

Measurement was made by the method described in the second invention.

(2) % Pentad and % Abnormal Insertion

Measurement was made by the method described in the second invention.

(3) Comonomer Unit Content (% by Mole) in Copolymer

Measurement was made by the method described in the second invention.

(4) Molecular Weight Distribution (Mw/Mn)

Measurement was made by the method described in the first invention.

(5) DSC Analysis

Measurement was made by the method described in the second invention.

(6) Temperature-Raising Fractional Chromatography

Measurement was made by the method described in the first invention.

(7) Tensile Modulus

Measurement was made by the method described in the second invention.

(8) Internal Haze

Measurement was made by the method described in the second invention.

(9) % Elasticity Recovery

The method described in JP-A-5-132590 was followed.

Thus, a propylenic polymer was press-molded and a JIS No. 2 dumb-belltest specimen was prepared. The constant-width region of the dumb-bellwas marked at 25 mm interval, which was designated as L0. The specimenwas stretched using a tensile test device from 80 mm to 160 mm of theinter-chuck distance at the stretching speed of 50 mm/min, and then theinter-chuck distance was allowed to become the initial length, and thenafter one minute the distance between the marks was determined anddesignated as L1. A % elasticity recovery was calculated by the equationshown below. When the value obtained was zero then the result was judgedas “No recovery”.

[(2L0−L1)/L0)×100

L0: Initial distance between marks on dumb-bell

L1: Distance between marks on dumb-bell after stretching

(10) Anti-Blocking Ability

A propylenic polymer was press-molded to obtain a test piece, which wasbound in the conditions described below and examined for its peelingstrength by a tensile test device.

Test piece: 15 cm×62.5 mm×2 mm

Binding conditions: Bound at 40° C. over the area of 15 mm×31 mm underthe pressing load of 0.7 kg for 3 hours.

Shear peeling conditions: Crosshead speed of 50 mm/min

(11) Izod Impact Strength

A propylenic polymer was press-molded to obtain a test piece which wassubjected to the test in accordance with JIS K-7110 with the test piecethickness of 3 mm at the ambient temperature of −5° C.

(12) Amount of Components Dissolved Out into Hexane (H25)

Measurement was made by the method described in the second invention.

(13) Boiling Diethylether Extract

Measurement was made by the method described in the first invention.

(14) Density

A density was determined in accordance with JIS K7112.

(15) Glass Transition Temperature (Tg)

A glass transition temperature (Tg) was determined in accordance withJIS K7198 (Tensile oscillation method) under the conditions specifiedbelow.

Frequency 10 Hz

Load 300 g

Temperature range −140° C. to 80° C.

(16) Vicat Softening Point

A Vicat softening point was determined in accordance with JIS K7206.

Example IV-1 (1) Preparation of Methyl Aluminoxane/Silica Carrier

A thoroughly nitrogen-purged 500 mL glass contained fitted with adropping funnel was charged with toluene (500 mL) and then with 4.04 gof a silica (indicated also as SiO₂) manufactured by FUJI SILICIA whichhad previously been sintered at 200° C. for 3 hours under nitrogen flowand the mixture was stirred at 400 rpm. At 0° C., a solution (29.8 mL)of a methyl aluminoxane (indicated also as MAO) manufactured byAlbemarle in toluene was added slowly over 45 minutes. The stirring wascontinued further for 1 hour at 0° C., 1 hour at room temperature andthen 4 hours at 80° C. After completion of the reaction, the mixture wasallowed to cool to 60° C. at which point the supernatant was washed bymeans of decantation three times with toluene (200 mL) and three timeswith heptane (200 mL) to obtain an intended product. The product wasstored as a heptane slurry in a Schlenk's bottle. The amount of aluminumsupported was 12.06% when determined by an UV quantification method.

(2) Synthesis of (dimethylsilylene) 2 (3-n-butylindenyl)2 zirconiumdichloride

The method similar to that described in Example II-1 in the secondinvention was employed.

(3) Synthesis of rac-Me2 Si(2-Et-4,5-BenzInd)2ZrCl2[racemi-dimethylsilylene bis(2-ethyl-4,5-benzoindenyl)zirconiumdichloride]

According to the description in JP-A-6-184179 and JP-A-7-196734, theprocedures of (I) to (VI) were employed for the synthesis.

Synthesis of diethyl-ethyl(2-naphthylmethyl)malonate (I)

7.63 g (320 mmol) of sodium is dissolved in 200 mL of absolute ethanolwith heating, and treated dropwise with 58.1 ml (310 mmol) ofdiethylethyl malonate at room temperature. A solution of 64 g (310 mmol)of 2-bromonaphthalene dissolved in 300 mL of ethanol is added dropwiseslowly at 0° C., and the reaction mixture is heated under reflux for 5hours. This is poured into an ice water, and extracted with ethylacetate.

The organic phase is dried over anhydrous sodium sulfate and the solventis distilled off. To the oily residue, 50 mL of hexane was added andcooled to 0° C. to obtain 7.12 g of Compound (I) (yield: 70%)

Synthesis of 2-ethyl-3-naphthylpropionic acid (II)

A solution of 33.8 g (603 mmol) of potassium hydroxide dissolved in 100mL of water is added dropwise to 49.3 g (150 mmol) of Compound (I) in150 mL of ethanol, and the reaction mixture is heated under reflux for 4hours. After distilling the solvent off, the solid obtained is combinedwith ethyl acetate and water and adjusted at pH1 with hydrochloric acid.After drying over anhydrous magnesium sulfate, the solvent of theorganic phase is distilled off. The residue is combined with hexane andstirred. The brown solid thus obtained is placed in a flask, which isheated at 175° C. After heating until termination of gas evolutionfollowed by cooling to room temperature, 30 g of Compound (II) wasobtained as a brown solid (yield: 87%).

Synthesis of 2-ethyl-6,7-benzoindan-1-on (III)

30 g (131 mmol) of Compound (II) is admixed with 29 mL of thionylchloride, and the mixture is heated under reflux for 30 minutes.Subsequently, an excessive thionyl chloride is distilled off underreduced pressure. To the residue, 50 mL of methylene chloride is added.The solution is added dropwise slowly to a suspension of 35 mg (262mmol) of aluminum trichloride in 100 mL of methylene chloride, and aftercompletion of the addition the mixture is further heated under refluxfor 30 minutes. The mixture is poured onto an ice, and extracted withmethylene chloride. The organic phase is dried over anhydrous sodiumsulfate and the solvent is distilled off. The brackish-brown oil issubjected to a column chromatography on silica gel using hexane/ethylacetate=8/2 as an eluent to obtain 11.3 g of Compound (III) (yield:41%).

Synthesis of 2-ethyl-4,5-benzoindene (IV)

In 400 mL of a solvent mixture of THF/methanol (2:1), 11.3 g (53.7 mmol)of indanone (III) is dissolved and admixed with 3.0 g (80.5 mmol) ofsodium borohydride in portions. The reaction mixture is stirred for 12hours at room temperature. The solution is poured onto an ice andhydrochloric acid is added. After extraction with ether, the organicphase is washed with water and dried over anhydrous sodium sulfate.After distilling the solvent off, an orange oil is dissolved in 300 mLof toluene, and the solution is heated together with 0.77 g (4.26 mmol)of p-toluenesulfonic acid at 80° C. for 15 minutes. After allowing tocool to room temperature followed by washing several times with waterfollowed by drying over anhydrous sodium sulfate, the solvent isdistilled off. The residue was subjected to a column chromatography onsilica gel using hexane/ethyl acetate=20/1 as an eluent to obtain 6.2 gof Compound (IV) as a colorless oil (yield: 59%).

Synthesis of dimethylbis(2-ethyl-4,5-benzoindenyl)silane (V)

6.2 g (31.7 mmol) of indene (IV) is dissolved in 50 m of THF, and 20.7mL (31.7 mmol, 1.53M solution in hexane) of n-butyllithium is addeddropwise. The reaction mixture is heated under reflux for 1 hour. Thesolution is added dropwise to a solution of 1.93 g (15 mmol) ofdimethyldichlorosilane in 10 mL of THF, and the mixture is heated underreflux for 6 hours. The reaction solution is hydrolyzed and extractedwith ether. The organic phase is dried over anhydrous sodium sulfate andthe solvent is distilled off. The residue is subjected to a columnchromatography on silica gel using hexane/ethyl acetate 3% as an eluent:to obtain 2.8 g of Compound (V) (yield: 41%).

Synthesis of rac-Me2 Si(2-Et-4,5-BenzInd)2ZrCl2 [racemi-dimethylsilylenebis(2-ethyl-4,5-benzoindenyl)zirconium dichloride] (VI)

2.8 g (6.3 mmol) of Compound (V) is admixed with 20 mL of THF andtreated dropwise with 10.3 mL (15.8 mmol, 1.53 M solution in hexane) ofn-butyllithium. The reaction mixture is stirred for 12 hours at roomtemperature. After distilling the solvent off, the residue is washedwith hexane. The powder thus obtained is dried under reduced pressure.This is suspended in 25 mL of methylene chloride and combined with 1.5 g(6.3 mmol) of zirconium tetrachloride suspended in 25 mL of methylenechloride. The reaction mixture is stirred for 12 hours at roomtemperature, and the solvent is distilled off and the residue isextracted with 20 mL of toluene. The residue of the toluene extract isextracted with methylene chloride, and the extract is concentrated andstored in a refrigerator to obtain 1.3 g of a metallocene (VI) (yield:35%).

(4) Preparation of Co-Supporting Catalyst

A thoroughly nitrogen-purged. 50 mL Schlenk's tube was charged undernitrogen flow with heptane (5 mL) and triisobutylaluminium (2M, 0.25 mL,0.5 mmol) followed by a slurry of MAO/SiO₂ carrier obtained above (0.37mol/L, 13.6 mL, 5 mmol, as Al) in heptane and a slurry ofbis-(dimethylsilylene)-bis-(3-n-butylindenyl)zirconium dichloride[(SiM2) (SiMe2) (3-n-BuInd)2ZrCl2] (5 μmol/mL, 2.5 mL, 12.5 μmol) inheptane, a slurry ofdimethylsilylene-bis(2-ethyl-4,5-benzoindenyl)zirconium dichloride[SiMe2(2-Et-4,5-BzInd) 2ZrCl2] (10 μmol/mL, 0.25 mL, 2.5 μmol) inheptane, and stirred at room temperature for 30 minutes to obtain aco-supporting catalyst (1).

(5) Vapor Phase Polymerization of Propylene

A 5 L autoclave was charged with 100 g of a polypropylene powder(homo-PP, 720 μm of greater in particle size) as a catalyst dispersantand dried under vacuum for 20 minutes at 70° C. After allowing to be atan atmospheric pressure with nitrogen, triisobutylaluminium (2M, 1.25mL, 25 mmol) was added under nitrogen flow with stirring (200 rpm).After stirring for 15 minutes, the co-supporting catalyst (1) preparedin Step (3) was added and the mixture was stirred for 5 minutes.Beginning at this time point (50° C., atmospheric pressure, 200 rpm),the temperature and the pressure were raised over 30 minutes to thereactor temperature of 70° C. and the propylene pressure of 28 kg/cm²Gwith stirring at 350 rpm, and then the vapor phase polymerization wascontinued further for 60 minutes. As a result, a powdery polymerundergoing no adhesion onto the wall was obtained. The yield was 260 g.The polymer thus obtained was extracted with diethylether as describedabove and the resin characteristics were measured. The results are shownin Table IV-1. In this table, Example 1 means Example IV-1. The sameapplies analogously to Example 2 or later as well as Comparatives.

Example IV-2 (1) Preparation of Supporting Catalyst (1)

A thoroughly nitrogen-purged 50 mL Schlenk's tube was charged undernitrogen flow with heptane (5 mL) and triisobutylaluminium (2M, 0.25 mL,0.5 mmol) followed by a slurry of MAO/SiO2 carrier obtained in ExampleIV-1, Step (1) (0.37 mol/L, 13.6 mL, 5 mmol, as Al) in heptane and aslurry of dimethylsilylene-bis(2-ethyl-4,5-benzoindenyl)zirconiumdichloride [SiMe2(2-Et-4,5-BzInd) 2ZrCl2] obtained in Example IV-1, Step(3) (10 mol/mL, 0.25 mL, 2.5 μmol) in heptane, and stirred at roomtemperature for 30 minutes to obtain a co-supporting catalyst (1).

(2) Vapor Phase Two-Step Polymerization Employing High StereoregularSupported Metallocene Catalyst in First Step and Low StereoregularSupported Metallocene Catalyst in Second Step <First StepPolymerization>

A 5 L autoclave was charged with 100 g of a polypropylene powder(homo-PP, 720 μm of greater in particle size) as a catalyst dispersantand dried under vacuum for 20 minutes at 70° C. After allowing to be atan atmospheric pressure with nitrogen, triisobutylaluminium (2M, 1.25mL, 25 mmol) was added under nitrogen flow with stirring (200 rpm).After stirring for 15 minutes, the co-supporting catalyst (1) preparedin Step (1) was added and the mixture was stirred for 5 minutes.Beginning at this time point (50° C., atmospheric pressure, 200 rpm),the temperature and the pressure were raised over 30 minutes to thereactor temperature of 70° C. and the propylene pressure of 28 kg/cm²Gwith stirring at 350 rpm, and then the vapor phase polymerization wascontinued further for 20 minutes.

<Second Step Polymerization>

Subsequently, a thoroughly nitrogen-purged 50 mL Schlenk's tube wascharged under nitrogen flow with toluene (10 mL) and a solution oftriisobutylaluminium (2M, 0.25 mL, 0.5 mmol) in heptane followed by aslurry of MAO/SiO₂ carrier obtained in Example IV-1, Step (1) (0.37mol/L, 6 mL, 2.5 mmol, as Al) in heptane and a slurry ofbis-(dimethylsilylene)-bis-(3-n-butylindenyl)zirconium dichloride[(SiM2)(SiMe2)(3-n-BuInd)2ZrCl2] obtained in Example IV-1, Step (2) (5μmol/mL, 0.1 mL, 0.5 μmol) in heptane, and stirred at room temperaturefor 5 minutes to obtain a co-supporting catalyst (2). This solution wasintroduced in an autoclave using a catalyst-introducing tube. Then thepolymerization was effected until the total pressure became 28 kg/cm²Gat 70° C. for 30 minutes. As a result, a powdery polymer undergoing noadhesion onto the wall was obtained. The yield was 200 g. The polymerthus obtained was examined for the diethyl-characteristics describedabove were measured. The results are shown in Table IV-1.

Example IV-3 (1) Preparation of Solid Catalyst Component

After purging a 5 L three-necked flask fitted with a stirrer with anitrogen gas, 500 mL of dehydrated heptane and 160 g (1.4 M) ofdiethoxymagnesium were added. The mixture was heated to 40° C., combinedwith 28.5 mL (225 mM) of silicon tetrachloride, stirred for 20 minutes,and then admixed with 25.2 mL (127 mM) of diethyl phthalate. Thesolution was heated to 80° C. and treated dropwise with 461 mL (4.2 M)of titanium tetrachloride using a dropping funnel, and then stirred atthe internal temperature of 110° C. for 2 hours to allow the catalyst tobe supported. Thereafter, the catalyst was washed thoroughly withdehydrated heptane. 768 ml (7M) of titanium tetrachloride was furtheradded and stirred at the internal temperature of 110° C. for 2 hourswhereby effecting the second supporting procedure. Thereafter, thecatalyst was washed thoroughly with dehydrated heptane to obtain SolidComponent A (supported Ti content−3.0% by weight).

(2) Preliminary Polymerization of Solid Catalyst Component

A nitrogen-purged 5 L three-necked flask fitted with a stirrer wascharged with a slurry of 60 g of the solid catalyst component (37.6mM-Ti) obtained above in heptane and also with dehydrated heptane tomake the entire volume 500 mL. The solution was stirred with being keptat 10° C., and combined with 24.8 mM of triethylaluminiun and 12.4 mM ofcyclohexylmethyldimethoxysilane. While still keeping the temperature at10° C., a predetermined amount of propylene was allowed to be absorbedfor 40 minutes, and the residual monomer was washed thoroughly withheptane with being purged with nitrogen, whereby obtaining 65 g of apreliminary polymerized catalyst B (seal level=0.083 g PP/g solidcatalyst).

(3) Two-Step Slurry Polymerization of Propylene Employing PreliminarilyPolymerized Mg—Ti-Based Catalyst in First Step and Low StereoregularMetallocene Catalyst in Second Step <First Step Polymerization>

A 1 L stainless steel autoclave fitted with a stirrer was driedthoroughly, purged with nitrogen, and then charged with 400 ml ofdehydrated heptane. 2 mM of triethylaluminium and 8.6 mg of Catalyst Bwere added, and hydrogen was introduced at 1 kg/cm²G, and then propylenewas introduced with raising the temperature and the pressure to 80° C.and 8 Kg/cm²G as a total pressure, followed by effecting polymerizationfor 20 minutes. Thereafter, the temperature was lowered to 50° C. andthe system was depressurized.

<Second Step Polymerization.

Subsequently, a thoroughly nitrogen-purged 50 mL Schlenk's tube wascharged under nitrogen flow with toluene (10 mL) and a solution oftriisobutylaluminium in heptane (2M, 0.5 mL, 1.0 mmol) followed by asolution of MAO in toluene (1.43M, 0.35 mL, 0.5 mmol) and a slurry ofbis-(dimethylsilylene)-bis-(3-n-butylindenyl)zirconium dichloride[(SiMe₂)(SiMe₂)(3-n-BuInd)2ZrCl₂ in heptane (5 mmol/mL, 0.5 mL, 2.5mol), and stirred at room temperature for 5 minutes to obtain Catalyst(3). This solution of catalyst was fed to an autoclave using acatalyst-introducing tube. The pressure of propylene was raised slowlyto 80 kg/cm²G as a total pressure, and the polymerization was effectedat 70° C. for 40 minutes. After completion of the reaction, unreactedpropylene was removed by depressurization. The reaction mixture waspoured into 2 L of methanol to precipitate polypropylene, which wasfiltered and dried to obtain 21 g of polypropylene. The polymer thusobtained was extracted with diethylether as described above and theresin characteristics were measured. The results are shown in TableIV-1.

Example IV-4 Two-Step Vapor Phase Polymerization of Propylene EmployingPreliminarily Polymerized Mg—Ti-Based Catalyst in First Step and LowStereoregular Metallocene Catalyst in Second Step <First StepPolymerization>

A 5 L autoclave was charged with 30 g of a polypropylene powder(homo-PP, 720 μm of greater in particle size) as a catalyst dispersantand dried under vacuum for 20 minutes at 70° C. After allowing to be atan atmospheric pressure with nitrogen, triethylaluminium (2M, 1.8 mL,3.6 mmol) was added under nitrogen flow with stirring (200 rpm). Afterstirring for 15 minutes, the reaction system was depressurized.

Thereafter, hydrogen was introduced at 3 kg/cm²G, and propylene gas wasintroduced until the total pressure became 28 kg/cm²G. Then a mixture ofheptane (10 mL), triethylaluminium (2M, 0.2 mL, 0.4 mmol) and Catalyst B(17.3 mg, Ti:0.01 mmol) was added via a catalyst-introducing tube, andthe vapor phase polymerization was effected for 20 minutes at 400 rpm.

<Second Step Polymerization>

Subsequently, the solution of Catalyst (3) prepared similarly as inExample IV-3, Step (3) was placed in the autoclave. The polymerizationwas effected further for 40 minutes at 70° C. and the total pressure of28 kg/cm²G. As a result, a powdery polymer undergoing no adhesion ontothe wall was obtained. The yield was 270 g. The polymer thus obtainedwas extracted with diethylether as described above and the resincharacteristics were measured. The results are shown in Table IV-1.

Example IV-5 Two-Step Slurry Polymerization of Propylene Employing HighStereoregular Metallocene Catalyst in First Step and Low StereoregularMetallocene Catalyst in Second Step <First Step Polymerization>

A 1 L stainless steel, pressure-resistant autoclave fitted with astirrer was heated to 80° C. and dried under reduced pressurethoroughly, and then it was allowed to be at atmospheric pressure with adry nitrogen and allowed to cool to room temperature. Under dry nitrogenflow, 400 mL of dried deoxygenated heptane and a solution oftriisobutylaluminium in heptane (2.0M, 0.5 mL, 1.0 mmol) were added andstirred at 350 rpm for a while. On the other hand, a thoroughlynitrogen-purged 50 mL Schlenk's bottle were charged under nitrogen flowwith toluene (10 mL) and a solution of triisobutylaluminium in heptane(2M, 0.5 mL, 1.0 mmol) and then with a solution of a MAO in toluene(1.43 M, 0.35 mL, 0.5 mmol) and a slurry ofdimethylsilylene-bis-(2-ethyl-4,5-benzoindenyl)zirconium dichloride[SiMe₂ (2-Et-4,5-BzInd)₂ZrCl2] obtained in Example IV-1, Step (3) inheptane (1 μmol/mL, 0.1 mL, 0.1 μmol), which were stirred at roomtemperature for 5 minutes. The catalyst slurry was placed rapidly in theautoclave. Subsequently, the stirring was initiated at 1200 rpm, and thepropylene pressure was raised slowly to 8.0 kg/cm²G as a total pressure,and at the same time the temperature was raised slowly to 50° C. Thepolymerization was effected for 20 minutes. Subsequently, unreactedpropylene was removed by depressurization.

(Second Step Polymerization)

A solution of Catalyst (3) prepared similarly as in Example IV-3, Step(3) was placed in the autoclave. Then the propylene pressure was raisedslowly to 8.0 kg/cm²G as a total pressure to effect polymerization for40 minutes at 50° C. After completion of the reaction, unreactedpropylene was removed by depressurization. The polymer thus obtained waspoured into 2 L of methanol to precipitate polypropylene, which wasfiltered and dried to obtain 31 g of polypropylene. The polymer thusobtained was extracted with diethylether as described above and theresin characteristics were measured. The results are shown in TableIV-1.

Example IV-6 Polymerization of Propylene Using Co-Catalyst

A 1 L stainless steel, pressure-resistant autoclave fitted with astirrer was heated to 80° C. and dried under reduced pressurethoroughly, and then it was allowed to be at atmospheric pressure with adry nitrogen and allowed to cool to room temperature. Under dry nitrogenflow, 400 mL of dried deoxygenated heptane and 1.0 mL (2.0 mmol) of asolution of triisobutylaluminium in heptane (2.0 M) were added andstirred at 350 rpm for a while. On the other hand, a thoroughlynitrogen-purged 50 mL Schlenk's bottle were charged under nitrogen flowwith toluene (10 mL) and a solution of triisobutylaluminium in heptane(2M, 0.5 mL, 1.0 mmol) and then with a solution of an MAO in toluene(1.43M, 0.35 mL, 0.5 mmol), an slurry ofbis-(dimethylsilylene)-bis-(3-n-butylindenyl)zirconium dichloride[(SiM2) (SiMe2) (3-n-BuInd)2ZrCl2] obtained in Example TV-1, Step (2) inheptane (5 μmol/mL, 0.1 mL, 0.5 μmol), and a slurry ofdimethylsilylene-bis-(2-ethyl-4,5-benzoindenyl)zirconium dichloride[SiMe2 (2-Et-4,5-BzInd)₂ZrCl2] obtained in Example IV-1, Step (3) inheptane (1 μmol/mL, 0.1 mL, 0.1 μmol), which were stirred at roomtemperature for 5 minutes. The catalyst slurry was placed rapidly in theautoclave.

Subsequently, the stirring was initiated at 1200 rpm, and the propylenepressure was raised slowly to 8.0 kg/cm² as a total pressure, and at thesame time the temperature was raised slowly to 50° C. The polymerizationwas effected for minutes. After completion of the reaction, unreactedpropylene was removed by depressurization. The reaction mixture waspoured into 2 L of methanol to precipitate polypropylene, which wasfiltered and dried to obtain 22 g of polypropylene. The polymer thusobtained was extracted with diethylether as described above and theresin characteristics were measured. The results are shown in TableIV-1.

Example IV-7 Propylenic Copolymer (1) Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

The method described in Example I-1 in the first invention was employed.

(2) Propylene/Ethylene Copolymerization

A 2 L stainless steel autoclave received 1.2 L of toluene, 1.5 mmol oftriisobutylaluminium, 10 (Al) mmol of a methyl aluminoxane (manufacturedby Albemarle) and 20 mol of(1,2′-ethylene)(2,1′-ethylene)bis(3-methylindenyl)zirconium dichlorideand the mixture was warmed to 30° C., and then an ethylene/propylene gasmixture (molar ratio of ethylene/propylene=1/100) was introduced. Anexcessive gas was vented so that the total pressure became 7.0 kg/cm²G,and the polymerization was effected for 60 minutes while keeping aconstant gas composition in the reaction system, and then the contentwas recovered and dried under reduced pressure to obtain a propyleniccopolymer. The polymer thus obtained was extracted with diethylether asdescribed above and the resin characteristics were measured. The resultsare shown in Table IV-1.

Example IV-8 (1) Propylene Polymerization

A 10 L stainless steel autoclave received 6 L of heptane, 6 mmol oftriisobutylaluminium, and a catalyst component obtained by bringing 5mmol of a methyl aluminoxane (manufactured by Albemarle) intopreliminary contact with 5 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-n-butylindenyl) 2zirconium dichloride in toluene for 5 minutes. After introducinghydrogen at 0.5 kg/cm²G, a propylene gas was introduced until the totalpressure became 8.0 kg/cm², and the propylene gas was supplied using apressure controller to keep a constant pressure during polymerization.After polymerizing at 50° C. for 30 minutes, the content was recoveredand dried under reduced pressure to obtain a propylene homopolymer.

(3) Formulation and Kneading

30 Parts by weight of the polypropylene homopolymer obtained above and70 parts by weight of a PE-based resin, EG8100 available from DowChemical (glass transition temperature Tg=−100° C.) were combined withthe following additives and extruded by a single-screw extruder(TSUKADAJUKISEISAKUSHO: Model TLC35-20) to granulate into a pellet.

(Formulation of Additives)

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppm

Phosphorus-based antioxidant: IRGAPHOS 168 available from Ciba SpecialtyChemicals: 1000 ppm

(4) Evaluation of Resin Characteristics and Physical characteristics

Evaluation was made by the methods described above. The results obtainedare shown in Tables VI-2 and VI-3.

Example IV-9 Resin Blend

The procedure similar to that in Example IV-8 was employed except forchanging the amounts of the propylene homopolymer of Example IV-8 andthe PE-based resin, EG8100 available from Dow Chemical (glass transitiontemperature Tg=−100° C.), to 60 parts by weight and 40 parts by weight,respectively. The results obtained are shown in Tables VI-3.

Example IV-10 Resin Blend

The procedure similar to that in Example IV-8 was employed except forusing 30 parts by weight of the propylene homopolymer of Example IV-8,40 parts by weight of Polypropylene E105GM available from IDEMITSUSEKIYU KAGAKU (Tc=110° C.) and 40 parts by weight a PE-based resin,EG8100 available from Dow Chemical (glass transition temperatureTg=−100° C.). The results obtained are shown in Tables VI-3.

TABLE IV-1 Item Example 1 Example 2 Example 3 Example 4 Example 5Example 6 Example 7 Entire Comonomer content, % — — — — — — 10 polymerby mole [η] dl/g 2.6 2.1 1.4 2.4 3.2 3.4 0.7 Boiling diethylether 25 199 22 27 15 56 extract, % by weight Diethylether % mmmm, % by mole 40 3941 39 42 39 — extract P, % by mole — — — — — — 76 components rrrr/(1 −mmmm) 0.04 0.04 0.04 0.04 0.04 0.04 — W25, % by weight 95 96 94 95 94 9556 Mw/Mn 2.3 2.2 2.4 2.2 2.3 2.3 6.1 [η] dl/g 2.6 2.5 3.9 2.6 4.1 3.80.8 Tm ° C. nd nd nd nd nd nd 76 ΔH J/mol nd nd nd nd nd nd 19 Tc ° C.nd nd nd nd nd nd 18 % 2, 1 insertion, % by 0 0 0 0 0 0 — mole % 1, 3insertion, % by 0 0 0 0 0 0 — mole (NOTE) nd: Not detected

TABLE IV-2 Propylene homopolymer produced in Example 8(a) Item (a)Comonomer content, % by mole — W25, % by weight 93 H25, % by weight 17Tm ° C. nd ΔH J/mol nd 6 × (Tm − 140) — [η] dl/g 2.5 Boilingdiethylether extract, % by 30 weight % mmmm, % by mole 41 P, % by mole —rrrr/(1 − mmmm) 0.04 Mw/Mn 2.4 % 2,1 insertion, % by mole 0 % 1,3insertion, % by mole 0 Tc ° C. nd (NOTE) nd: Not detected

TABLE IV-3 Example Item Example 8 Example 9 10 Formulation Component(a), % by weight 30 60 30 ratio EG8100, % by weight 70 40 30 E105GM, %by weight — — 40 Resin Comonomer content, % by mole — — — composition[η] dl/g 2.6 2.1 1.4 Boiling diethylether extract, % by 25 19 9 weightPhysical Tensile modulus MPa 20 25 150 characteristics % Elasticityrecovery % 69 64 10 Izod impact strength KJ/m² No break No break Nobreak Vicat softening point ° C. 42 50 90 (NOTE) Izod impact strength:Determined at −30° C. with notches being formed

[Fifth Invention]

A method for evaluating the resin characteristics and the filmperformance in this invention are described below.

(1) Intrinsic Viscosity [η]

Measurement was made by the method described in the second invention.

(2) % Pentad and % Abnormal Insertion

Measurement was made by the method described in the second invention.

(3) Molecular WEIGHT DISTRIBUTION (Mw/Mn)

Measurement was made by the method described in the first invention.

(4) DSC Analysis

Measurement was made by the method described in the second invention.

(5) Temperature-Raising Fractional Chromatography

Measurement was made by the method described in the first invention.

(6) Tensile Modulus

Measurement was made by the method described in the first invention.

(7) Amount of Components Dissolved Out into Hexane (H25)

Measurement was made by the method described in the second invention.

“Film Qualification”

A film once formed was annealed at 40° C. for 24 hours and thenconditioned at a temperature of 23±2° C. and a humidity of 50±10% for 16hours or longer and subsequently qualified at the same temperature andhumidity.

(1) Heat Seal Temperature and Heat Seal Strength

A test was conducted in accordance with JIS Z-1707. Typically, under theconditions specified below, a heat seal bar whose temperature wascorrected as being read by a surface thermometer was used to seal a filmwhich was then allowed to stand at room temperature overnight andexamined for the peeling strength (heat seal strength) by a type-Tpeeling method at the peeling speed of 200 mm/min at room temperature.The heat seal temperature was defined as the temperature at which thepeeling strength was 300 g/15 mm, and calculated on the basis of a curveof a seal strength vs peeling strength.

Sealing Conditions

Seal surface: Metal roll surface/metal roll surfaceSeal area: 15×10 mmSeal pressure: 2.0 kg/cm²Seal duration: 1 secondSeal temperature: Several temperatures over the range which include theheat seal temperature to be calculated later

(2) Haze

A test was conducted in accordance with JIS K-7105.

(3) Tensile Modulus

A tensile test was conducted under the conditions specified below inaccordance with JIS K-7127.

Crosshead speed: 500 mm/minLoad cell: 10 kgDirection: Machine direction

(4) Frequency Distribution Determination of Melt Viscoelasticity

A rotary rheometer manufactured by RHEOMETRIX is used together with acone plate (25 mm in diameter, 0.10 radian in cone angle) at thetemperature of 175° C. with the initial strain of 20% to perform thefrequency distribution determination of the melt viscosity. A complexmodulus of elasticity G* (iω) at a frequency (ω(rad/sec)) can berepresented by a stress σ* and a strain γ* as shown below.

G*(iω)=σ*/γ*=G′(ω)+iG″(ω)

wherein i is an imaginary number unit.

Example V-1 (1) Catalyst Preparation Synthesis of (dimethylsilylene)2(3-n-butylindenyl)2 zirconium dichloride

The method described in Example II-1 in the second invention wasemployed.

(2) Propylene Polymerization

A 10 L stainless steel autoclave received 6 L of heptane, 6 mmol oftriisobutylaluminium, and a catalyst component obtained by bringing 5mmol of a methyl aluminoxane (Albemarle) into preliminary contact with 5μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(3-n-butylindenyl)₂zirconium dichloride in toluene for 5 minutes. After introducinghydrogen at 0.5 kg/cm²G, a propylene gas was introduced until the totalpressure became 8.0 kg/cm², and the propylene gas was supplied using apressure controller to keep a constant pressure during polymerization.After polymerizing at 50° C. for 30 minutes, the content was recoveredand dried under reduced pressure to obtain a propylene homopolymer(B-1).

(3) Formulation and Kneading

The polypropylene homopolymer (B-1) obtained above was combined with thefollowing additives and extruded by a single-screw extruder(manufactured by TSUKADA

JUKISEISAKUSHO: Model TLC35-20) to granulate into a pellet.

(Formulation of Additives)

Phenolic antioxidant: IRGANOX 1010 available from Ciba SpecialtyChemicals, 1000 ppmPhosphorus-based antioxidant: P-EPQ available from Ciba

Specialty Chemicals: 500 ppm

Neutralizing agent: Calcium stearate: 500 ppmNeutralizing agent: DHT-4A: 500 ppm

(4) Production of Resin Composition

15 Parts by weight of the propylenic polymer [a-1] produced as describedabove as a propylenic polymer [I] and 85 parts by weight of IDEMITSUPOLYPRO F-704NP as a crystalline propylenic polymer [II] were placed ina blender and mixed thoroughly, and then extruded by a single-screwextruder (manufacture by TSUKADA JUKISEISAKUSHO: Model TLC35-20) wherebyeffecting granulation.

(5) Film Forming

From the pellet of the propylenic resin composition thus obtained, afilm whose thickness was 50 μm was formed using a mmφ molding machinemanufactured by TSUKADA JUKISEISAKUSHO with the T die exit resintemperature of 190° C., the chill roll temperature of 30° C. and thehaul-off speed of 6 m/min.

(6) Evaluation of Resin Characteristics and Physical Characteristics

Evaluation was made by the methods described above. The results obtainedare shown in Tables V-1 and V-2. In these tables, Example 1 meansExample V-1. The same applies analogously to Example 2 or later as wellas Comparative Examples.

Example V-2

The method similar to that in Example V-1 was employed except forchanging the blend ratios of the propylenic polymer [a-1] and IDEMITSUPOLYPRO F-704 NP to 30 parts by weight and 70 parts by weight,respectively. The results are shown in Table V-2.

Example V-3

The method similar to that in Example V-1 was employed except forchanging the blend ratios of the propylenic polymer [a-1] and IDEMITSUPOLYPRO F-704 NP to 60 parts by weight and parts by weight,respectively. The results are shown in Table V-2.

Comparative Example V-1

The method similar to that in Example V-1 was employed except for usingan ethylene-propylene copolymer rubber available from NIPPON SYNTHETICRUBBER KK (Grade: EP913Y) instead of the propylenic polymer [a-1]. Theresults are shown in Table V-2.

Comparative Example V-2

The method similar to that in Example V-2 was employed except for usingan ethylene-propylene copolymer rubber available from NIPPON SYNTHETICRUBBER KK (Grade: EP913Y) instead of the propylenic polymer [a-1]. Theresults are shown in Table V-2.

Comparative Example V-3

The method similar to that in Example V-3 was employed except for usingan ethylene-propylene copolymer rubber available from NIPPON SYNTHETICRUBBER KK (Grade: EP913Y) instead of the propylenic polymer [a-1]. Theresults are shown in Table V-2.

Comparative Example V-4

The method similar to that in Example V-1 was employed except for usingonly IDEMITSU POLYPRO F-704NP without blending a propylenic polymer [I].The results are shown in Table V-2.

Comparative Example V-5

The method similar to that in Example V-1 was employed except for usingonly IDEMITSU POLYPRO F-454NP without blending a propylenic polymer [I].The results are shown in Table V-2.

Comparative Example V-6

The method similar to that in Example V-1 was employed except for usingonly IDEMITSU TPO E2900 without blending a propylenic polymer [I]. Theresults are shown in Table V-2.

TABLE V-1 Propylenic polymer (I) (a-1) W25, % by weight 93 H25, % byweight 17 ΔH J/mol nd 6 × (Tm − 140) — % mmmm, % by mole 41 rrrr/(1 −mmmm), % by mole 4 % 2,1 insertion, % by mole 0 % 1,3 insertion, % bymole 0 Mw/Mn 2.4 [η] dl/g 2.5 Tm ° C. nd Tc ° C. nd Tensile modulus MPa31 (NOTE) n.d.: Not detected

TABLE V-2 Com- Com- Com- Com- Com- Com- parative parative parativeparative parative parative Example-1 Example-2 Example-3 Example-1Example-2 Example-3 Example-4 Example-5 Example-6 Formulation Propylenicpolymer (I), (a-1) (a-1) (a-1) EP913Y EP913Y EP913Y — — — ratio (% byweight) Crystalline propylenic 15 30 60 15 30 60 0 0 0 polymer (II), (%by weight) Resin ΔHm (J/g) F-704NP F-704NP F-704NP F-704NP F-704NPF-704NP F-704NP F-454NP E2900 characteristics Tc (° C.) 85 70 40 85 7040 100 100 100 (¼)ΔHm + 90 88 73 41 83 62 38 100 87 72 ω(G′ = G″)(rad/sec) 115.2 112.3 106.1 111.9 111.9 112.2 112.4 113.8 106.4 (1/10)ΔHm + 15 112.1 108.3 100.3 110.7 105.5 99.6 115.1 111.7 108.1 FilmHaze (%) 1.8 1.8 3.6 2.1 11.0 5.5 1.6 61.0 13.5 performance Tensilemodulus (Mpa) 741 518 166 873 612 343 1040 856 486 Heat seal temperature152 144 130 145 138 129 155 154 158 (° C.) Heat seal strength (gf/15 mm)Seal temperature 115° C. 63 Seal temperature 120° C. 116 Sealtemperature 125° C. 199 Seal temperature 130° C. 269 322 Sealtemperature 135° C. 628 298 293 Seal temperature 140° C. 111 1031 209302 344 Seal temperature 145° C. 333 1289 303 306 372 Seal temperature150° C. 137 695 1505 455 329 339 155 124 88 Seal temperature 155° C. 4941359 1699 971 389 381 256 345 99 Seal temperature 160° C. 1449 2920 2020916 486 461 1052 600 443 Seal temperature 165° C. 3900 3087 2147 939 411444 2484 1682 1553 Seal temperature 170° C. 3453 3353 483 3105 2646 3641Seal temperature 175° C. 3662 525 3690 3479

[Sixth Invention]

Respective tests and evaluations were made as described below.

[1] Intrinsic Viscosity [η]

Measurement was made by the method described in the first invention.

[2] Molecular Weight Distribution (Mw/Mn)

Measurement was made by the method described in the first invention.

[3]% Isotactic Pentad

A % isotactic pentad (% mmmm, % by mole) means the proportion (%) of thepropylene structure units each having a meso-structure (mmmm structurein which 5 methyl groups are aligned in the same direction) in 5propylene structure units based on the assignment of the peaks in a¹³C-NMR spectrum as described by Cheng H. N., Ewen J. A., Macromol.cem., 1989, 190, 1350, and was determined using the following device andthe conditions.

Instrument: Nippon Densi Model JNM-EX400 NMR deviceSample concentration: 220 mg/NMR Solvent 3 ml

NMR Solvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10 vol %)Temperature: 130° C. Pulse gap: 45°

Pulse interval: 4 secondsNumber of cycles: 10000 times[4] When a % Isotactic Pentad (% mmmm, % by Mole) and a Melting Point(Tm° C.) are in the Relationship Represented by Formula (I):

Tm≦[mmmm]+65  (I)

then the result was judged as OK, and when not the result was judged asNO.

[5] Tensile Modulus

A tensile test in accordance with JIS K-7127NI was employed. The testwas conducted at the crosshead speed of 500 mm/min in the machinedirection (MD).

[6] When a Tensile Modulus (TM (MPa)) and a Heat Seal Temperature (HST(° C.)) are in the Relationship Represented by Formula (II):

TM≧22×HST−1850  (XI)

then the result was judged as OK, and when not the result was judged asNO.

[7] Film Impact (F.I.)

A film impact means a impact destruction strength, and was determinedusing a film impact tester produced by TOYOSEIKI together with a 1-inchimpact head.

[8] Heat Seal Temperature (HST)

A heat seal temperature (HST) was determined in accordance with JISK-1707. After sealing under the fusing conditions described belowfollowed by allowing to stand at room temperature overnight, the peelingstrength was determined by a type-T peeling method at the peeling speedof 200 mm/min at room temperature to obtain a curve of a seal strengthvs peeling strength, from which the temperature at which the peelingstrength became 3003 g/15 mm was calculated and designated as the heatseal temperature.

Fusing Condition

Seal duration: 2 secondsSeal area: 15×10 mmSeal pressure: 5.3 kg/cm²Seal temperature: Several temperatures over the range which include theheat seal temperature to be calculated later

The temperature of a heat seal bar is corrected to the value read by asurface thermometer.

[9] Melting Point (Tm° C.) and Crystallization Temperature (Tc° C.) ofResin

Using a differential scanning calorimeter (Perking Elmer, DSC-7), 10 mgof a sample is fused for 3 minutes at 230° C. under a nitrogenatmosphere and then the temperature is lowered to 0° C. at the rate of10° C./minute. The peak top of the maximum peak in the crystallizationexothermic curve obtained during this course was regarded as thecrystallization temperature (Tc° C.). After holding at 0° C. for 3minutes, the temperature is raised at the rate of 10° C./minute toobtain a fusion endothermic curve, in which the peak top of the maximumpeak was regarded as the melting point (Tm° C.).

[10] Criteria for Eutectic Based on Direct Fusion Endothermic curve offilm sample

A eutectic formation of a polymer in this invention is judged to havetaken place when the peak top, observed in a fusion endothermic curveobtained by subjecting 10 mg of a film sample which had just beencast-molded to a differential scanning calorimetry (Perking Elmer,DSC-7) under nitrogen atmosphere in which the temperature was kept at 0°C. for 3 minutes and then raised at 10° C./min, is single.

In an actual determination, the peak observed may have two or moreresolved peak tops derived from melting points of resin components asthe constituents of the film, or may have a single peak top associatedoptionally with the shoulder or trace peaks possibly derived from thecomponents other than the resin components. Accordingly, the result isindicated as: ◯: which indicates the eutectic formation when a singlepeak top with or without overlapping shoulders or traces is observed;and,

x: which indicates no eutectic formation when two or more peak tops withor without overlapping shoulders or traces is observed.

Example VI-1 (1) Production of Component (A-1)

A 10 L stainless steel autoclave was charged with 4.0 L of toluene, 8mmol of triisobutylaluminium and 20 μmol oftetrakis-pentafluorophenylborate dimethylanilinium salt, and the mixturewas heated to 40° C. and combined with 10 mmol of hydrogen, and thenpropylene was introduced until the total pressure became 7.0 kg/cm²-G.At this point, 5 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)hafnium dichloride was addedand the polymerization was initiated. Propylene was supplied via apressure controller to keep a constant pressure. After 2 hours, thecontent was recovered, dried under reduced pressure to obtain 820 g ofpolypropylene.

The polypropylene thus obtained had the meso-pentad fraction (mmmm (inpercentage terms by mole)) of 91%, the intrinsic viscosity [η] of 1.5dl/g and the molecular weight distribution (Mw/Mn ratio) of 1.9.

(2) Production of Component (B-1)

A 1 L stainless steel autoclave was charged with 400 mL of toluene, 1mmol of triisobutylaluminium and 4 mol oftetrakis-pentafluorophenylborate dimethylanilinium salt and the mixturewas heated to 55° C. and combined with 4 mmol of hydrogen, and thenpropylene was introduced until the total pressure became 7.0 kg/cm²-G.At this point, 1 mmol of(1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)hafnium dichloride was addedand the polymerization was initiated. Propylene was supplied via apressure controller to keep a constant pressure. After 1 hours, thecontent was recovered, and poured into a large amount of methanol,filtered and dried to obtain 75 g of polypropylene.

The polypropylene thus obtained had the meso-pentad fraction (mmmm (inpercentage terms by mole)) of 90%, the intrinsic viscosity [η] of 0.5dl/g and the molecular weight distribution (Mw/Mn ratio) of 2.0.

(3) Formulation and Kneading

91 parts by weight of the component A-1 and 9 parts by weight of thecomponent B-1, in combination with antioxidants, namely, 750 ppm byweight of IRGANOX 1010 (manufacture by Ciba Specialty Chemicals, tradename) and 750 ppm by weight of IRGANOX 168 (manufactured by CibaSpecialty Chemicals, trade name), and 500 ppm by weight of calciumstearate as a neutralizing agent, 1000 ppm by weight of erucic acidamide as a slipping agent, and 1800 ppm by weight of a silica-basedanti-blocking agent as an anti-blocking agent were kneaded by asingle-screw extruder (manufactured by TSUKAD AJUKISEISAKUSHO: ModelTLC35-20) to obtain a resin composition.

(4) Film Forming

By means of a T die cast molding method and using a 20 mmφ T die castmolding machine manufactured by TSUKADA JUKISEISAKUSHO, a film whosethickness was 25 μm was formed under the conditions specified below.After a film was formed at the T die exit temperature of 191° C., thechill roll temperature of 30° C., and the haul-off speed of 6 m/min, itwas aged at 40° C. for 24 hours.

The film thus obtained was examined for the tensile modulus, the filmimpact and the heat seal temperature together with the film moldingstability, and the results are shown in Table VI-1. In this table,Example 1 means Example VI-1. The same applies analogously to Example 2or later as well as Comparative Examples. The film molding stability wasvery satisfactory, and adverse events such as neck-in were not observed.

Example VI-2

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using the component (A-1) in the amount of 90%by weight instead of 91% by weight and using 10 parts by weight of thecomponent (B-2) instead of 9 parts by weight of the component (B-1). Theresults are shown in Table VI-1.

The film molding stability was very satisfactory, and adverse eventssuch as neck-in were not observed. No blisters were observed.

Production of Component (B-2) 1) Preparation of Magnesium Compound

A reaction chamber fitted with a stirrer (whose capacity was 500 L) waspurged thoroughly with a nitrogen gas, and charged with 97.2 kg ofethanol, 640 g of iodine and 6.4 kg of elemental magnesium, and themixture was reacted under reflux with stirring until the evolution of ahydrogen gas from the reaction system ceased, whereby obtaining a solidreaction product. The fluid reaction mixture containing this solidproduct was dried under reduced pressure to obtain an intended magnesiumcompound.

2) Preparation of Solid Catalyst Component

A reaction chamber fitted with a stirrer (whose capacity was 500 L)purged sufficiently with a nitrogen gas was charged with 30 kg of themagnesium compound obtained above (not pulverized), 150 L of purifiedheptane (n-heptane), 4.5 L of silicon tetrachloride and 5.4 L ofdi-n-butyl phthalate. The reaction system was kept at 90° C., and 144 Lof titanium tetrachloride was added with stirring and the reaction wascontinued at 110° C. for 2 hours and then the solid components wereseparated and washed with a purified heptane at 80° C. Addition of 288 Lof titanium tetrachloride followed by the reaction at 110° C. for 2hours followed by a sufficient washing with a purified heptane at 80° C.yielded a solid catalyst component.

3) Pretreatment

A 500 L reaction chamber fitted with a stirrer was charged with 230 L ofa purified heptane (n-heptane), and fed with 25 kg of the solid catalystcomponent obtained above, and 1.0 mol/mol of triethylaluminium and 1.8mol/mol of dicyclopentyldimehtoxysilane, both per titanium atom of thesolid catalyst component. Subsequently, propylene was introduced at thepartial pressure of 0.3 kg/cm²G, and the reaction was continued for 4hours at 25° C. After completion of the reaction, the solid catalystcomponent was washed several times with a purified heptane, and fedfurther with carbon dioxide and stirred for 24 hours.

4) Main Polymerization

A 200 L polymerization reactor fitted with a stirrer was charged withpropylene, and also fed with 3 mmol/kg-PP, as titanium atom in the solidcatalyst component, of the catalyst component, 4 mmol/kg-PP oftriethylaluminium and 1 mmol/kg-PP of dicyclopentyldimethoxysilane, andthen the mixture was reacted at the polymerization temperature of 80° C.and the polymerization pressure (total pressure) of 28 kg/cm²G. In thisExample, the hydrogen supply was adjusted so that the intended molecularweight was achieved. The polymer (B) thus obtained had the % isotacticpentad of 97.6 mol % and the melt index of 5.9 g/10 minutes. Analysis(gas chromatography) of the composition of the gas in the polymerizationreactor during polymerization revealed that the hydrogen concentrationwas 4.2% by mole.

Example VI-3

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using 90% by weight of the component (A-2)instead of 91% by weight of the component (A-1) and also using 10 partsby weight of the component (B-2) instead of 9 parts by weight of thecomponent (B-1). The results are shown in Table VI-1.

The film molding stability was very satisfactory, and the release fromthe chill roll was also satisfactory. No blisters were observed.

Production of Component (A-2) 1)(1,2′ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

The method similar to that in Example I-1 in the first invention wasemployed.

2) Polymerization

A 10 L stainless steel autoclave was charged with 5 L of heptane, 5 mmolof triisobutylaluminium, and a catalyst component obtained by bringing19 mmol as Al of a methyl aluminoxane (manufactured by Albemarle) intopreliminary contact with 19 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichlorideprepared above in toluene for 30 minutes, and the temperature was raisedto 40° C. and the propylene gas was introduced until the total pressurebecame 8.0 kg/cm²G. During polymerization, the propylene gas wassupplied using a pressure controller to keep a constant pressure, andafter 1 hour the content was recovered and dried under reduced pressureto obtain polypropylene.

Comparative Example VI-1

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using only the component (A-1) withoutincorporating the component (B-1). The results are shown in Table VI-1.Upon film-forming, neck-in was observed.

Comparative Example VI-2

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using only the component (A-2) withoutincorporating the component (B-1). The results are shown in Table VI-1.The release of the film from the chill roll was very poor, and the filmcould not be molded.

Comparative Example VI-3

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using E2900 produced by IDEMITSU SEKIYU KAGAKUwhich was obtained using a non-metallocene catalyst(titanium/magnesium-based catalyst) instead of the components (A-1) and(B-1). The results are shown in Table VI-1. Although the film moldingcould be performed satisfactorily, the chill roll tended to be spotted.

Comparative Example VI-4

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using 50% by weight of the component (A-2)instead of 91% by weight of the component (A-1) and also using 50 partsby weight of the component (B-2) instead of 9 parts by weight of thecomponent (B-1). The results are shown in Table VI-1.

Although the film molding could be performed satisfactorily withoutexhibiting particular adverse events, several blisters were observed.

Comparative VI-5

A resin was prepared and a film was formed and evaluated similarly as inExample VI-1 except for using the component (A-1) in the amount of 95%by weight instead of 91% by weight and using 5 parts by weight of a highdensity polyethylene (manufactured by IDEMITSU SEKIYU KAGIAKU,IDEMITSUHDPE 640UF) instead of 9 parts by weight of the component (B-1).The results are shown in Table VI-1.

Although the film molding could be performed satisfactorily withoutexhibiting particular adverse events, substantial blisters formed madethe determination of the physical characteristics impossible.

TABLE VI-1 Com- Com- Com- Com- Com- parative parative parative parativeparative Example 1 Example 2 Example 3 Example 1 Example 2 Example 3Example 4 Example 5 Reference Example Composition Component 91 90 100 95(%) A (A-1) Component 90 100 45 A (A-2) Component 9 100 B (B-1)Component 10 10 55 100 B (B-2) Others 100 (E2900) HDPE 5 100 (640UF)Component A Intrinsic viscosity [η] dl/g 1.5 1.5 1.2 1.5 1.2 1.9 1.2 1.5— — — Molecular weight distribution 1.9 1.9 1.8 1.9 1.8 2.6 1.8 1.9 — —— [Mw/Mn] % mmmm, % by mole 91.0 91.0 63.5 91.0 63.5 72.7 63.5 91.0 — —— Melting point (Tm ° C.) 146.5 146.5 104.0 146.5 104.0 160.0 104.0146.5 — — — Tm ≦ [mmmm] + 65 OK OK OK OK OK NO OK OK Component BIntrinsic viscosity [η] dl/g 0.5 1.7 1.7 — — — 1.7 3.4 0.5 1.7 3.4Molecular weight distribution 2.0 4.2 4.2 — — — 4.2 22 2.0 4.2 22[Mw/Mn] Resin composition and film Melting point (Tm ° C.) 146.3 147.0108.0/16 146.5 104.0 160.0 163.5/11 146/130 145.5 165.5 130Crystallization temperature — — — 107.0 63.5 117.0 — — 109.8 117.0 116(Tc ° C.) Tensile modulus (TM: Mpa) 1100 1100 550 1100 — 514 880 — — — —Heat seal temperature (HST: 130 130 102 135 — 151 130 — — — — ° C.) TM ≧22 × HST − 1850 OK OK OK NO — NO NO — — — — Film impact (1 inch) J/m29000 28000 NB 29000 — NB 2700 — — — — Moldability No neck-in No MoldingNeck-in Molding Molding Molding Molding — — — neck-in possibleimpossible possible possible possible Eutectic formation ∘ ∘ ∘ ∘ ∘ ∘ ∘ x— — —

[Seventh Invention]

The methods for evaluating the resin characteristics, for film-formingand for qualifying a film are discussed below.

(A) Method for Evaluating Resin Characteristics

1) 1-Octene Unit Content (% by mole) in Copolymer and StereoregularlityIndex (P(% by Mole))

The 1-octene unit content (% by mole)) in the copolymer was obtained inaccordance with the following equation (1) from the spectrum determinedby the ¹³C-NMR.

$\begin{matrix}{{1 - {{Octene}\mspace{14mu} {unit}\mspace{14mu} {content}}} = {\frac{\left( {{{I\lbrack 2\rbrack}/2} + {I\lbrack 4\rbrack}} \right)}{\begin{Bmatrix}{{I\lbrack 1\rbrack} + {I\lbrack 2\rbrack} + {I\lbrack 3\rbrack} +} \\{{I\lbrack 4\rbrack} + {2 \times \lbrack 11\rbrack}}\end{Bmatrix}} \times 100}} & (1)\end{matrix}$

Also in accordance with the following equation (2), a stereoregularityindex (P (% by mole)) of the copolymer was obtained.

$\begin{matrix}{P = \frac{\left( {I\lbrack 16\rbrack} \right) \times 100}{\left\{ {{I\lbrack 16\rbrack} + {I\lbrack 17\rbrack} + {I\lbrack 18\rbrack}} \right\}}} & (2)\end{matrix}$

wherein [1], [2] and the like represent the signals of a spectrum of arandom copolymer of propylene and 1-octene determined by ¹³C-NMR. I[1],I[2] and the like represent the respective signal intensities. Thesignals of a spectrum of a random copolymer of propylene and 1-octenedetermined by ¹³C-NMR are indicated in Table VII-1.

Instead of the signal of a PPP chain Sαβ carbon which was difficult tobe determined because of the overlapping signal of PPP chain Tαβ carbon,the signal intensity of a PPP chain Sαβ carbon was indicated as analternative.

A ¹³C-NMR spectrum was obtained using Nippon Densi Model JNM-EX400 NMRdevice under the conditions specified below.

Sample concentration: 220 mg/3 ml NMR solventNMR Solvent: 1,2,4-Trichlorobenzene/benzene-d6 (90/10 vol)Determination temperature: 130° C.

Pulse gap: 45° C.

Pulse interval: 4 secondsNumber of cycles: 4000 times

2) 1-Dodecene Unit Content (% by Mole) in Copolymer andStereoregularlity Index (P(% by Mole))

The 1-dodecene unit content (% by mole)) in the copolymer was obtainedin accordance with the following equation (3) from the spectrumdetermined by the ¹³C-NMR.

$\begin{matrix}{{1 - {{Dodecene}\mspace{14mu} {unit}\mspace{14mu} {content}}} = \frac{\left( {{{I\lbrack 2\rbrack}/2} + {I\lbrack 4\rbrack}} \right) \times 100}{\left\{ {{I\lbrack 1\rbrack} + {I\lbrack 2\rbrack} + {3 \times {I\lbrack 3\rbrack}} + {I\lbrack 4\rbrack}} \right\}}} & (3)\end{matrix}$

Also in accordance with the following equation (4), a stereoregularityindex (P (% by mole)) of the copolymer was obtained.

$\begin{matrix}{P = \frac{\left( {I\lbrack 5\rbrack} \right) \times 100}{\left\{ {{I\lbrack 5\rbrack} + {I\lbrack 6\rbrack} + {I\lbrack 7\rbrack}} \right\}}} & (4)\end{matrix}$

wherein [1], [2] and the like represent the signals of a spectrum of arandom copolymer of propylene and 1-dodecene determined by ¹³C-NMR.I[1], I[2] and the like represent the respective signal intensities. Thesignals of a spectrum of a random copolymer of propylene and 1-dodecenedetermined by ¹³C-NMR are indicated in Table VII-2.

Because of the difficulty in resolving the signal of a PPP chain Sαβcarbon from the overlapping signal of PPP chain Tαβ carbon and thesignal of a PPP chain Sαβ carbon from the overlapping signal of the sidechain methylene carbon of a 1-dodecene unit, the signal intensity of aPPP chain Sαα carbon was employed as a substitute.

3) 1-Decene Unit Content (% by Mole) in Copolymer and StereoregularlityIndex (P(% by Mole))

The 1-decene unit content (% by mole)) and the stereoregularlity index(P(% by mole)) of the copolymer were obtained by the method similar tothat in above 2) except for using Table VII-3 indicating the signals ofa spectrum of a random copolymer of propylene and 1-decene by the¹³C-NMR instead of Table VII-2.

Because of the difficulty in resolving the signal of a PPP chain Sαβcarbon from the overlapping signal of PPP chain Tαβ carbon and thesignal of a PPP chain Sαβ carbon from the overlapping signal of the sidechain methylene carbon of a 1-decene unit, the signal intensity of a PPPchain Sαα carbon was employed as a substitute.

4) Ethylene Unit Content (% by Mole) in Copolymer and StereoregularlityIndex (P(% by Mole))

The ethylene unit content (% by mole)) in the copolymer was obtained inaccordance with the following equation (5) from the spectrum determinedby the ¹³C-NMR.

Ethylene unit content=E/S×100  (5)

wherein S and E are each represented as follows:

S=IEPE+IPPE+IEEE+IPPP+IPEE+IPEP

E=IEEE+2/3(IPEE+IEPE)+1/3(IPPE+IPEP)

wherein:

IEPE=I(12) IPPE=I(15)+I(11)+(I(14)−I(11))/2+I(10) IEEE=I(18)/2+I(17)/4IPPP=I(19)+(I(6)+I(7))/2+I(3)+I(13′)+I(11)+(I(14)−I(11))/2 IPEE=I(20)IPEP=(I(8)+I(9)−2×(I(11))/4+I(21).

A stereoregularity index (P(% by mole)) of the copolymer was obtainedaccording to the equation (6) shown below.

P=Im/I×100  (6)

wherein Im and I are each represented as follows:

Im=I(22)

I═I(22)+I(23)+I(24)−{(I(8)+I(9))/2+I(10)+3/2×I(11)+I(12)+I(13)+I(15)}.

In the equation shown above, (1), (2) and the like are the signals of aspectrum of a random copolymer of propylene and ethylene obtained by¹³C-NMR, and I(1), I(2) and the like represent the intensities ofrespective signals. The signals of a spectrum of a random copolymer ofpropylene and ethylene determined by ¹³C-NMR are shown in Table VII-4.

5) 1-Butene Unit Content (% by Mole) in Copolymer and StereoregularlityIndex (P(% by Mole))

The 1-butene unit content (% by mole)) in the copolymer was obtained inaccordance with the following equation (7) from the spectrum determinedby the ¹³C-NMR.

$\begin{matrix}{{1 - {{Butene}\mspace{14mu} {unit}\mspace{14mu} {content}}} = {\frac{\left( {{{I\lbrack 2\rbrack}/2} + {I\lbrack 4\rbrack}} \right)}{\begin{Bmatrix}{{I\lbrack 1\rbrack} + {I\lbrack 2\rbrack} + {I\lbrack 3\rbrack} +} \\{{I\lbrack 4\rbrack} + {2 \times {I\lbrack 9\rbrack}}}\end{Bmatrix}} \times 100}} & (7)\end{matrix}$

Also in accordance with the following equation (8), a stereoregularityindex (P (% by mole)) of the copolymer was obtained.

$\begin{matrix}{P = \frac{\left( {I\lbrack 12\rbrack} \right) \times 100}{\left\{ {{I\lbrack 12\rbrack} + {I\lbrack 13\rbrack} + {I\lbrack 14\rbrack}} \right\}}} & (8)\end{matrix}$

wherein [1], [2] and the like represent the signals of a spectrum of arandom copolymer of propylene and 1-butene determined by ¹³C-NMR. I[1],I[2] and the like represent the respective signal intensities. Thesignals of a spectrum of a random copolymer of propylene and 1-butenedetermined by ¹³C-NMR are indicated in Table VII-5.

The signal of a PPP chain Sαβ carbon was substituted with the signalintensity of a PPP chain Sαβ carbon.

6) Main Elution Peak Temperature (Tp), Half of Main Elution PeakTemperature (Th), Elution Level at 0° C. (WO) and Elution Level inTemperature Range from (Tp−5)° C. to (Tp+5)° C.

A temperature-raising fractional chromatography (TREF) obtained usingthe devices, the procedure and the conditions specified below.

Tp: Peak top temperature of main elution peak in elution curveW0: % By weight of component which are dissolved out instead of beingadsorbed onto a packing at the column temperature of 0° C. based on thetotal weightWP: % By weight of component which are dissolved out instead of beingadsorbed onto a packing in the temperature range of (Tp−5)° C. to(Tp+5)° C. based on the total weightW(TP+10): % By weight of component which are dissolved out instead ofbeing adsorbed onto a packing at a column temperature not lower than(Tp+10)° C. based on the total weight

A) Operating Procedure

A sample solution is introduced into a TREF column adjusted at 135° C.and then the temperature is lowered gradually at the lowering rate of 5°C./hour to 0° C. to allow the sample to be adsorbed onto the packing.Subsequently, the column temperature was raised at the raising rate of40° C./hour to 135° C. to obtain an elution curve.

B) Instruments

TREF column: Manufactured by GL SCIENCE, Silica gel column (4.6×150 mm)Flow cell: Manufactured by GL SCIENCE, pathlength 1 mm, KBr cellFeed pump: Manufactured by SENSHU KEAGAKU, Pump Model SSC-3100Valve oven: Manufactured by GL SCIENCE, Oven model 554TREF oven: Manufactured by GL SCIENCEDual-system thermostat: Manufactured by RIKAGAKU KOGYO, Thermostat modelREX-C100Detector: Infrared detector for HPLC, Manufactured by FOXBORO CORP.,Model MIRAN 1A CVF10-way valve: Manufactured by VALCO, Electric valve

Loop: Manufactured by VALCO, 500 L Loop C) Operating Conditions

Solvent: o-DichlorobenzeneSample concentration: 7.5 g/LInjection volume: 500 μLPumping rate: 2.0 mL/minDetection wavenumber: 3.41 μmColumn packing: CHROMOSOLVE P (30 to 60 mesh)Column temperature deviation: Within 0.2° C.7) Intrinsic Viscosity ([η] dl/g) determined in decalin at 135° C.

Measurement was made by the method described in the first invention.

8) Crystallization Temperature (Tc(° C.)) and Melting Point (Tm(° C.))Determined by Differential Scanning Microscopy

Measurement was made by the method described in the first invention.

9) Criteria for Eutectic Based on Crystallization Exothermic Curve ofFilm Sample

A eutectic formation of a polymer in this invention is judged to havetaken place when the peak top of the maximum peak, observed in acrystallization exothermic curve obtained as described in above 8) bysubjecting a film sample which had just been cast-molded to adifferential scanning calorimetry (Perkin Elmer, DSC-7), is a singlepeak and at the same time the crystallization temperature of this filmis higher than that of a component (A′) and lower than that of acomponent (B′).

10) Molecular Weight Distribution Mw/Mn Ratio

Measurement was made by the method described in the first invention.

(B) Film-Forming Method

From a pellet of the propylenic resin in Examples and Comparativesdescribed below, a film whose thickness was 30 μm was formed using a 20mmφ molding machine manufactured by TSUKADAJUKISEISAKUSHO under themolding conditions specified below.

T die exit resin temperature: 192° C.Haul-off speed: 6.0 m/minChill roll temperature: 30° C.Chill roll: Mirror

(C) Film Qualification

A film once formed was subjected to aging at 40° C. for 24 hoursfollowed by conditioning at a temperature of 23±2° C. and a humidity of50±10% for 16 hours or longer and then qualified at the same temperatureand humidity.

1) Heat Seal Performance

A test was conducted in accordance with JIS Z-1707. The fusingconditions were as indicated below. The temperature of the heat seal barwas corrected as being read by a surface thermometer. After sealingfollowed by allowing to stand at room temperature overnight, the peelingstrength was determined by a type-T peeling method at the peeling speedof 200 mm/min at room temperature. The heat seal temperature wasobtained as a temperature at which the peeling strength was 300 g/15 mmby calculating on the basis of a curve of a seal strength vs peelingstrength.

Seal duration: 1 secondSeal area: 15 mm×15 mmSeal pressure: 2.0 kg/cm²Seal temperature: Several temperatures over the range which include theheat seal temperature to be calculated later

2) Anti-Blocking Ability

A rectangular film (30 cm×15 cm) was fixed on a mount whose size was 10cm×10 cm and fused under the conditions specified below, andsubsequently the peeling strength was determined.

Fusing condition 1, Temperature:60° C., Duration: 3 hours, Load: 36g/cm², Area:10 cm×10 cmFusing condition 2, Temperature:50° C., Duration: 1 week, Load: g/cm²,Area:10 cm×10 cm

The peeling test was conducted under the conditions shown below.

Test speed: 20 mm/minLoad cell: 2 kg

3) Slipperiness

A sled on which a film was applied was allowed to stand on a glass plateon which the film was also applied, and then the glass plate was tiltedand the tangent of the angle θ at which the sled began to slip wasdetermined. The friction angle meter manufactured by TOYOSEIKI wasemployed in the test under the conditions specified below.

Slipping surface: Metal roll surface/metal roll surfaceTilting speed: 2.70/secSled weight: 1 kgSled sectional area: 65 cm²Interface pressure: 15 g/cm²

4) Haze

A test was conducted in accordance with JIS K-7105.

5) Tensile Modulus

A tensile test was conducted under the conditions specified below inaccordance with JIS K-7127.

Crosshead speed: 500 mm/minLoad cell: 10 kgDirection: Machine direction (MD)6) When a tensile modulus (TM (MPa)) and a heat seal temperature (HST(°C.)) are in the relationship represented by Formula (II):

TM≧22×HST−1850  (II)

then the result was judged as OK, and when not the result was judged asNO.

Example VII-1 Production of Copolymer (A′-1) [1] Preparation of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloride

The method similar to that in Example I-1 in the first invention wasemployed.

[2] Polymerization (propylene-1-butene copolymer)

A 10 L stainless steel autoclave was charged with 5 L of heptane, 5 mmolof triisobutylaluminium, 50 g of 1-butene, and a catalyst componentobtained by bringing 19 mmol, as aluminum, of a methyl aluminoxane(Albemarle) into preliminary contact with 19 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconium dichloridein toluene for 30 minutes, and the mixture was heated to 40° C. and thepropylene gas was introduced until the total pressure became 8.0 kg/cm²G. During polymerization, the propylene gas was supplied using apressure controller to keep a constant pressure, and after 1 hour thecontent was recovered and dried under reduced pressure to obtain apropylenic copolymer.

The copolymeric powder thus obtained was combined with the followingadditives and extruded by a kneader into a pellet.

1) Antioxidant

IRGANOX 1010 available from Ciba-geigy: 1000 ppm and,IRGAPHOS 168 available from Ciba-geigy: 1000 ppm2) Neutralizing agent . . . Calcium stearate: 1000 ppm3) Anti-blocking agent . . . Silica-based agent: 1800 ppm4) Slipping agent . . . Erucic acid amid: 500 ppm

A copolymer pellet thus obtained was examined for its resincharacteristics by the method in Section (A) described above.

Propylenic Polymer (B′) 1) Preparation of Magnesium Compound

A reaction chamber fitted with a stirrer (whose capacity was 500 L) waspurged thoroughly with a nitrogen gas, and charged with 97.2 kg ofethanol, 640 g of iodine and 6.4 kg of elemental magnesium, and themixture was reacted under reflux with stirring until the evolution of ahydrogen gas from the reaction system ceased, whereby obtaining a solidreaction product. The fluid reaction mixture containing this solidproduct was dried under reduced pressure to obtain an intended magnesiumcompound.

2) Preparation of Solid Catalyst Component

A reaction chamber fitted with a stirrer (whose capacity was 500 L)purged sufficiently with a nitrogen gas was charged with 30 kg of themagnesium compound obtained above (not pulverized), 150 L of purifiedheptane (n-heptane), 4.5 L of silicon tetrachloride and 5.4 L ofdi-n-butyl phthalate. The reaction system was kept at 90° C., and 144 Lof titanium tetrachloride was added with stirring and the reaction wascontinued at 110° C. for 2 hours and then the solid components wereseparated and washed with a purified heptane at 80° C. Addition of 288 Lof titanium tetrachloride followed by the reaction at 110° C. for 2hours followed by a sufficient washing with a purified heptane at 80° C.yielded a solid catalyst component.

3) Pretreatment

A 500 L reaction chamber fitted with a stirrer was charged with 230 L ofa purified heptane (n-heptane), and fed with 25 kg of the solid catalystcomponent obtained above, and 1.0 mol/mol of triethylaluminium and 1.8mol/mol of dicyclopentyldimehtoxysilane, both per titanium atom of thesolid catalyst component. Subsequently, propylene was introduced at thepartial pressure of 0.3 kg/cm²G, and the reaction was continued for 4hours at: 25° C. After completion of the reaction, the solid catalystcomponent was washed several times with a purified heptane, and fedfurther with carbon dioxide and stirred for 24 hours.

4) Main Polymerization

A 200 L polymerization reactor fitted with a stirrer was charged withpropylene, and also fed with 3 mmol/kg-PP, as titanium atom in the solidcatalyst component, of the catalyst component, 4 mmol/kg-PP oftriethylaluminium and 1 mmol/kg-PP of dicyclopentyldimethoxysilane, andthen the mixture was reacted at the polymerization temperature of 80° C.and the polymerization pressure (total pressure) of 28 kg/cm². In thisExample, the hydrogen supply was adjusted so that the intended molecularweight was achieved. The polymer (B) thus obtained had the % isotacticpentad of 97.6 mol % and the melt index of 5.9 g/10 minutes. Analysis(gas chromatography) of the composition of the gas in the polymerizationreactor during polymerization revealed that the hydrogen concentrationwas 4.2% by mole.

The propylenic polymer powder thus obtained was combined with thefollowing additives and extruded by a kneader into a pellet.

1) Antioxidant

IRGANOX 1010 available from Ciba-geigy: 1000 ppm and,IRGAPHOS 168 available from Ciba-geigy: 1000 ppm2) Neutralizing agent . . . Calcium stearate: 1000 ppm3) Anti-blocking agent . . . Silica-based agent: 1000 ppm4) Slipping agent . . . Erucic acid amid: 1000 ppm

A propylenic polymer pellet thus obtained was examined for its resincharacteristics by the method in Section (A) described above.

90 Parts by weight of the copolymer (A′-1) thus obtained was mixedthoroughly with 10 parts by weight of the propylenic polymer (B′) by adry blender. The propylenic resin thus obtained was formed into a filmby the method in Section (B) described above, and qualified by themethod in Section (C) described above. The results are shown in TableVII-6. In this table, Example 1 means Example VII-1. The same appliesanalogously to Example 2 or later as well as Comparatives.

[Comparative VII-1]

A film was formed and evaluated by the method similar to that in ExampleVII-1 except for using only the component (A′-1) without using thecomponent (B′). The results are shown in Table VII-6.

Example VII-2 Production of Copolymer (A′-2) [1] Catalyst Preparation[1] Production of ethyl (2-indenyl)acetate

Under nitrogen flow, 3.3 g of sodium hydride was suspended in 300 mL oftetrahydrofurane and cooled to 10° C.

To this suspension, a solution of 28.3 g of ethyldiethylphosphonoacetatein 200 mL of tetrahydrofuran was added dropwise over 1 hour. Then themixture was stirred at room temperature for 30 minutes and then cooledon ice, and then treated dropwise with a solution of 16.33 g of2-indanone in 75 mL of tetrahydrofuran over 1 hour. Subsequently, themixture was stirred at room temperature for 30 minutes and then combinedwith water to effect hydrolysis followed by extraction with 500 mL ofdiethylether to separate the organic phase, whose solvent was distilledoff under reduced pressure. The residue was distilled under reducedpressure to obtain a pale yellow oil.

The oil obtained was identified as ethyl (2-indenyl)acetate on the basisof ¹H-NMR. The yield was 11.06 g.

[2] Production of 2-(2-indenyl)-ethanol

Under nitrogen flow, 2.2 g of lithium aluminum hydride was suspended in100 mL of dietylether. To this suspension, a solution of 11 g of ethyl(2-indenyl)acetate obtained in Step [1] described above in 50 mL ofdiethylether was added dropwise over 1 hour. After stirring for 30minutes at room temperature followed by cooling on ice, 50 mL of waterwas added portionwise, and then a dilute hydrochloric acid was added todissolve insolubles. The organic phase was separated and the solvent wasdistilled off under reduced pressure to obtain a white solid.

The compound obtained was identified as 2-(2-indenyl)-ethanol on thebasis of ¹H-NMR. The yield was 7.89 g.

[3] Production of 1-bromo-2-(2-indenyl)ethane

Under nitrogen flow, 4.61 g of 2-(2-indenyl)-ethanol obtained in Step[2] described above was dissolved in 65 mL of dichloromethane. To thissolution, 7.66 g of triphenylphosphine was added and then 5.19 g ofN-bromosuccinimide was added portionwise. After stirring at roomtemperature for 30 minutes followed by addition of water, the organicphase was separated and dried over anhydrous magnesium sulfate. Thesolvent was distilled off under reduced pressure and the residue waspurified on a silica gel column (eluted with hexane) to obtain acolorless oil.

This colorless oil was identified as 1-bromo-2-(2-indenyl)ethane on thebasis of ¹H-NMR. The yield was 5.07 g.

[4] Production of (1,2′-ethylene)(2,1′-ethylene)-bis(indene)

Under nitrogen flow, 50 mL of tetrahydrofuran was combined with 6.87 mLof diisopropylamine and cooled to −78° C. TO this solution, 1.96 mL of a1.64 mol/L solution of n-butyllithium in hexane was added dropwise over10 minutes. Subsequently, the reaction mixture was allowed to warm to 0°C., whereby obtaining a lithium diisopropylamide (LDA) solution.

Subsequently, under nitrogen flow, 500 mL of tetrahydrofuran wascombined with 11.69 g of 1-bromo-2-(2-indenyl)ethane obtained in Step[3] described above and stirred for dissolution followed by cooling to−78° C. This solution was treated dropwise over 30 minutes with the LDAsolution obtained above which had been cooled to −78° C., and thenallowed to warm to room temperature and then stirred for 12 hours.

To this reaction mixture, 500 mL of water was added to wash the organicphase, which was then dried over anhydrous magnesium sulfate. Then thesolvent was distilled off under reduced pressure to obtain a solid,which was purified by sublimation at 0.2 Torr at 150° C. to obtain awhite solid.

The compound thus obtained was identified as(1,2′-ethylene)(2,1′-ethylene)-bis(indene) on the basis of a fielddesorption mass spectrum (FD-MS) and ¹H-NMR.

[5] Production of dilithium salt of(1,2′-ethylene)(2,1′-ethylene)-bis(indene)

Under nitrogen flow, 0.6 g of (1,2′-ethylene)(2,1′-ethylene)-bis(indene)obtained in Step [4] described above was combined with 100 mL ofdiethylether and stirred and cooled to −78° C. This was treateddropwise, with 2.6 mL of a 1.64 mol/L solution of n-butyllithium inhexane over 30 minutes. The reaction mixture was allowed to warm to roomtemperature, stirred for 12 hours, and the solvent was distilled offunder reduced pressure to obtain a residue, which was washed twice with50 mL of hexane and dried under reduced pressure to obtain a dilithiumsalt of (1,2′-ethylene)(2,1′-ethylene)-bis(indene) as a pale yellowpowder.

[6] Production of (1,2′-ethylene)(2,1′-ethylene)-bis(indene) hafniumdichloride

Under nitrogen flow, 0.58 g of hafnium tetrachloride was suspended in100 mL of toluene and cooled to −78° C. Then this suspension was treatedover 30 minutes with 0.54 g of the dilithium salt of(1,2′-ethylene)(2,1′-ethylene)-bis(indene), obtained in Step [5]described above, suspended in 50 mL of toluene at −78° C.

This reaction mixture was allowed to warm to room temperature andstirred for 12 hours, and then toluene supernatant was filtered off andthe filter cake was extracted twice with 50 mL of dichloromethane andthe solvent was distilled off under reduced pressure. The residue wasrecrystallized from dichloromethane/hexane to obtain(1,2′-ethylene)(2,1′-ethylene)-bis(indene) hafnium dichloride. The yieldwas 0.18 g.

This compound was subjected to ¹H-NMR analysis and the following resultswere obtained.

¹H-NMR (CDCl₃): 3.66(8H), 6.37 (s, 2H), 6.90-7.60 (m, 8H)

This compound had the structure shown below.

[2] Polymerization (propylene-ethylene copolymer)

A 10 L stainless steel autoclave was charged with 6 L of toluene, 6 mmolof triisobutylaluminium, 20 μmol of tetrakis-pentafluorophenylboratedimethylanilinium salt and 5 μmol of(1,2′-ethylene)(2,1′-ethylene)-bis(indene) hafnium dichloride, and themixture was heated to 50° C. and the gas mixture ofethylene/propylene=10/100 was introduced until the total pressure became7.0 kg/cm²G. During polymerization, the propylene was supplied using apressure controller to keep a constant pressure, and after 3 hours thecontent was recovered and dried under reduced pressure to obtain apropylenic copolymer.

The copolymeric powder thus obtained was combined with the followingadditives and extruded by a kneader into a pellet.

1) Antioxidant

IRGANOX 1010 available from Ciba-geigy: 1000 ppm and,IRGAPHOS 168 available from Ciba-geigy: 1000 ppm2) Neutralizing agent . . . Calcium stearate: 1000 ppm3) Anti-blocking agent . . . Silica-based agent: 1800 ppm4) Slipping agent . . . Erucic acid amid: 500 ppmA copolymer pellet thus obtained was examined for its resincharacteristics by the method in Section (A) described above.

80 Parts by weight of the copolymer (A′-2) thus obtained was mixedthoroughly with 20 parts by weight of the propylenic polymer (B′-1) by adry blender.

The propylenic resin thus obtained was formed into a film by the methodsimilar to that in Section (B) described above except for setting thechill roll temperature at 60° C., and the film was qualified by themethod in Section (C) described above.

The results are shown in Table VII-6.

[Comparative VII-2]

A film was formed and evaluated by the method similar to that in ExampleVII-2 except for using only the component (A′-2) without using thecomponent (B′). The results are shown in Table VII-6.

Example VII-3 Production of Copolymer (A)

A 10 L stainless steel autoclave received 5.0 L of toluene, 6 mmol oftriisobutylaluminium and 500 mL of 1-octene, and charged with 40 μmol oftetrakis-pentafluorophenylborate dimethylanilinium salt and 20 mol ofracemidimethylsilyl-bis-2-ethyl-4,5-benzoindenylzirconium dichloride andthe mixture was heated to a propylene gas was introduced until the totalpressure became 8.0 kg/cm²G whereby initiating polymerization. Duringpolymerization, the propylene was supplied using a pressure controllerto keep a constant pressure. After 3 hours, the content was recoveredand dried under reduced pressure to obtain a copolymer.

The copolymeric powder thus obtained was combined with the followingadditives and extruded by a kneader into a pellet.

1) Antioxidant

IRGANOX 1010 available from Ciba-geigy: 1000 ppm and,IRGAPHOS 168 available from Ciba-geigy: 1000 ppm2) Neutralizing agent . . . Calcium stearate: 1000 ppm3) Anti-blocking agent . . . Silica-based agent: 1800 ppm4) Slipping agent . . . Erucic acid amid: 500 ppmA copolymer pellet thus obtained was examined for its resincharacteristics by the method in Section (A) described above.

Production of Propylenic Polymer (B)

The method similar to that for the propylenic polymer (B′) in ExampleVII-1 was employed.

80 Parts by weight of the copolymer (A) thus obtained was mixedthoroughly with 20 parts by weight of the propylenic polymer (B) by adry blender.

The propylenic resin thus obtained was formed into a film by the methodsimilar to that in Section (B) described above and the film wasqualified by the method in Section (C) described above. The results areshown in Table VII-6.

Example VII-4

The propylenic polymer (B) was produced by the method similar to thatfor the propylenic polymer (B′) in Example VII-1, except for adjustingthe amounts of ethylene and hydrogen supplied so that the predeterminedethylene content and molecular weight were achieved in the mainpolymerization. The polymer (B) thus obtained had the ethylene contentof 3.0% by mole, the % isotactic pentad of 99.2% by mole and the meltindex of 8.5 g/10 min. In this example, analysis (gas chromatography) ofthe composition of the gas in the polymerization reactor duringpolymerization revealed that the ethylene concentration was 1.2% by moleand the hydrogen concentration was 4.3% by mole. Thereafter, theprocedure similar to that in Example VII-3 was conducted except forchanging the amounts of the copolymer (A) and the propylenic polymer(B), obtained above, into 90 parts by weight and 10% by weight,respectively. The results are shown in Table VII-6.

Example VII-5

The method similar to that in Example VII-4 was employed except forsetting the chill roll temperature at 60° C. upon film-forming. Theresults are shown in Table VII-6.

Example VII-6

The copolymer (A) was produced by the method similar to that in ExampleVII-3 except for changing the amount of 1-octene from 500 mL to 300 mL,the polymerization temperature from 50° C. to 40° C. and using n-heptaneinstead of toluene with regard to the copolymer (A), and otherwise theprocedure in Example VII-3 was followed entirely. The results are shownin Table VII-6.

Example VII-7

The copolymer (A) was produced by the method similar to that in ExampleVII-3 except for using 500 mL of 1-dodecene instead of 1-octene,changing the polymerization temperature from 50° C. to 40° C. and usingn-heptane, instead of toluene with regard to the copolymer (A), andotherwise the procedure in Example VII-3 was followed entirely. Theresults are shown in Table VII-6.

Example VII-8

The copolymer (A) was produced by the method similar to that in ExampleVII-3 except for using 500 mL of 1-decene instead of 1-octene, changingthe polymerization temperature from 50° C. to 40° C. and using n-heptaneinstead of toluene with regard to the copolymer (A), and otherwise theprocedure in Example VII-3 was followed entirely. The results are shownin Table VII-6.

Comparative Example VII-3

The procedure similar to that in Example VII-3 was conducted except forusing 45 parts by weight of the copolymer (A) produced in Example VII-3and 55 parts by weight of the propylenic polymer (B) produced in ExampleVII-3. The results are shown in Table VII-6.

Comparative Example VII-4

A film was formed at the chill roll temperature of 60° C. using only thecopolymer (A) produced in Example VII-3 without using the propylenicpolymer (B). As a result, the release from the chill roll was poor and afilm having good appearance could not be obtained.

Comparative Example VII-5

Except for setting the chill roll temperature upon film-forming at 30°C. similarly as in Example VII-3, the procedure similar to that inComparative Example VII-4 was followed.

Example VII-9

The copolymer (A) was produced by the method similar to that in ExampleVII-3 except for using 500 mL of 1-butene instead of 1-octene and usingn-heptane instead of toluene with regard to the copolymer (A), andotherwise the procedure in Example VII-3 was followed entirely. Theresults are shown in Table VII-6.

Example VII-10

Except for subjecting a propylenic resin obtained from the same amountsof the copolymer (A) instead of the copolymer (A′-2) produced in ExampleVII-2 and the propylenic polymer (B) instead of the propylenic polymer(B′-1) used in Example VII-2 to the chill roll temperature of 30° C.,the procedure similar to that in Example VII-2 was followed. The resultsare shown in Table VII-6.

Reference Example

A commercially available linear low density polyethylene (manufacturedby IDEMITSU MORETEC V0398CN) was combined with the additives similarlyas in Example VII-3, and evaluated similarly as in Example VII-3. Theresults are shown in Table VII-6.

TABLE VII-1 Assignments of signals of ¹¹C-NMR of 1-octene/PP copolymer

(NOTE) P represents a propylene unit, and P represents a reversedpropylene unit, O represents a 1-octene unit. (NOTE) A chemical shift isrepresented in ppm.

TABLE VII-2 Chemical shifts and assignments of signals used incalculation of α and P of 1-dodecene/PP copolymer Number Chemical shiftAssignment 1 46.0-47.6 PP Sαα 2 43.8-44.4 PD Sαα 3 42.3 PPP Sαα 4 41.5DD Sαα 5 21.2-22.7 Pββ 6 20.6-21.2 Pββ 7 19.8-20.6 Pββ (Note) Drepresents a 1-dodecene unit. (Note) A chemical shift is represented inppm.

TABLE VII-3 Chemical shifts and assignments of signals used incalculation of α and P of 1-decene/PP copolymer Number Chemical shiftAssignment 1 46.0-47.6 PP Sαα 2 43.8-44.4 PD Sαα 3 42.3 PPP Sαα 4 41.5DD Sαα 5 21.2-22.7 Pββ 6 20.6-21.2 Pββ 7 19.8-20.6 Pββ (Note) Drepresents a 1-dodecene unit. (Note) A chemical shift is represented inppm.

TABLE VII-4 Assignments of signals of 13C-NMR spectrum of ethylene/PPcopolymer Chemical Number shift Assignment 1 45.1-47.3 PPP Sαα 2 42.3PPP Sαα 3 38.6 PPP Tαγ 4 38.0 Sαγ 5 37.5 Sαδ 6 36.0 PPP Sαβ 7 36.0 PPPTαβ 8 34.9 EPP, PEP Sαβ 9 34.6 EPP, PEP Sαβ 10 34.1 EPP Tγγ 11 33.7 EEPPTγδ 12 33.3 EPE Tδδ 13 31.6 PPP Tβγ 14 31.4 EPP Tβγ 15 31.0 PPE Tβδ 1630.7 PPP Sαβ 17 30.5 PEEE Sγδ 18 30.0 EEE Sδδ 19 29.0 PPP Tββ 20 27.3PEE Sβδ 21 24.6 PEP Sαβ 22 21.3-22.7 Pββ 23 20.6-21.3 Pββ 24 19.8-20.6Pββ 25 17.6 Pαβ 26 17.2 Pαγ (Note) E represents an ethylene unit. (Note)A chemical shift is represented in ppm.

TABLE VII-5 Assignments of signals of ¹³C-NMR spectrum of 1-butene/PPcopolymer Chemical Number shift Assignment 1 45.7-47.4 PP Sαα 243.0-44.9 PB Sαα 3 42.3 PPP Sαα 4 40.3 BB Sαα 5 38.6 PPP Tαγ 6 36.0 PPPSαβ and PPP Tαβ 7 35.5 B unit Tββ 8 31.6 PPP Tβγ 9 30.6 PPP Sαβ 1028.6-29.8 P unit Tββ 11 27.8-28.4 B unit side chain methylene carbon 1221.2-22.7 Pββ PPP(mm), PPB(mm), PBP(mm) 13 20.6-21.2 Pββ PPP(mr),PPB(mr), BPB(mr), PPB (rr), BPB(rr) 14 19.8-20.6 Pββ PPP(rr) 15 17.6 Pαβ16 17.2 Pαγ 17 11.1 B unit side chain methyl carbon (NOTE) B denotes a1-butene unit. (NOTE) A chemical shift is represented in ppm.

TABLE VII-6 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Example 7 Example 8 Resin Comonomer type 1-Butene Ethylene 1-Octene1-Octene 1-Octene 1-Octene 1- 1-Decene char- Dodecene acteristics α mol% 0.9 8.7 4.0 4.0 4.0 3.2 3.8 4.4 of copolymer [η] dl/g 1.2 1.7 1.5 1.51.5 1.7 1.9 1.9 A or A′ Tm ° C. 100.1 110.9 108.0 108.0 108.0 114.0108.7 103.9 Tc ° C. 59.1 75.8 67.8 67.8 67.8 74.6 67.0 63.2 P mol % 76.097.8 96.4 96.4 96.4 97.5 97.0 97.4 Tp ° C. 60.2 71.6 64.7 64.7 64.7 70.664.3 61.4 Wo wt % 1.10 0.64 0.69 0.69 0.69 0.59 1.08 1.06 Wp wt % 75.368.7 90.8 90.8 90.8 91.7 88.2 89.1 Mw/Mn 2.1 2.0 — — — — — — B or B′ Tm° C. 165.9 165.9 165.9 150.6 150.6 165.9 165.9 165.9 Tc ° C. 117.0 117.0117.0 106.9 106.9 117.0 117.0 117.0 Ratio A/B 90/10 80/20 80/20 90/1090/10 80/20 80/20 80/20 Chill roll temperature ° C. 30 60 30 30 60 30 3030 Film Heat seal temperature (HST: ° C.) 105 110 102 100 103 108 101100 performance Anti-blocking, Condition 1 (N/m²) 48 82 45 46 41 38 3943 Anti-blocking, Condition 2 (N/m²) 23 45 24 26 21 19 20 24Slipperiness tan θ 0.35 0.39 0.26 0.21 0.19 0.38 0.29 0.31 Haze % 1.91.8 1.0 1.1 1.6 1.5 1.2 1.0 Tensile modulus (TM: MPa) 370 360 540 510560 670 530 480 TM ≧ 22 × HST − 1850 ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Moldability Noneck-in No neck-in No No No No No No neck-in neck-in neck-in neck-inneck-in neck-in resence/absence of eutectic ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ formation86.0 104.7 98.3 96.2 96.2 103.8 98.0 94.2 Tc ° C. ComparativeComparative Comparative Comparative Comparative Reference Example 1Example Example Example Example Example 9 Example 10 Example ResinComonomer type 1-Butene Ethylene 1-Octene 1-Octene 1-Octene 1-ButeneEthylene Commercially characteristics available LL of copolymer α mol %0.9 8.0 4.0 4.0 4.0 9.0 8.7 4.1 A or A′ [η] dl/g 1.2 1.7 1.5 1.5 1.5 2.21.7 1.3 Tm ° C. 100.1 110.9 108.0 108.0 108.0 121.9 110.9 102.7 Tc ° C.59.1 75.8 67.8 67.8 67.8 84.3 75.8 88.5 P mol % 76 97.8 96.4 96.4 96.497.6 97.8 — Tp ° C. — — 64.7 64.7 64.7 79.1 71.6 69.3 Wo wt % 2.0 0.640.69 0.69 0.69 0.34 0.64 2.64 Wp wt % — — 90.8 90.8 90.8 86.8 68.7 57.4Mw/Mn 2.1 2.0 — — — 2.1 2.0 — B or B′ Tm ° C. — — 165.9 — — 165.9 165.9— Tc ° C. — — 117.0 — — 117.0 117.0 — Comarative Comarative ComarativeComarative Comarative Example Reference Example 1 Example 2 Example 3Example 4 Example 5 Example 9 10 Example Ratio A/B 100/0 100/0 45/55100/0 100/0 80/20 80/20 100/0 Chill roll temperature ° C. 30 60 30 30 3030 Film Heat seal temperature — — 135 — 100 118 108 99 performance (HST:° C.) Anti-blocking, Condition 1 — — 25 — 42 40 87 129 (N/m²)Anti-blocking, Condition 2 — — 5 — 20 19 49 53 (N/m²) Slipperiness tan θ— — 0.29 — 0.29 0.24 0.41 0.87 Haze % — — 3.8 — 1.0 3.6 1.3 1.4 Tensilemodulus — — 900 — 490 600 310 110 (TM: MPa) TM ≧ 22 × HST − 1850 — — x —∘ x x x Moldability Molding Molding No neck-in Molding No neck-in No NoNo impossible impossible impossible neck-in neck-in neck-inresence/absence of eutectic — — ∘ — — ∘ ∘ — formation 114.3 105.5 104.7Tc ° C. (NOTE) Anti-blocking ability Condition 1: Fusing conditioninvolving the temperature of 60° C., the duration of 3 hours and theload of 36 g/cm² G, Anti-blocking ability Condition 2: Fusing conditioninvolving the temperature of 50° C., the duration of 1 week and the loadof 15 g/cm² G (1) (2) Example 9, (3) Reference Example, (4) Resincharacteristics of copolymer A or A′, (5) Comonomer type, (6) B or B′,(7), (8), (9), (10), (11)

[Eighth Invention]

The present invention is discussed specifically in the followingexamples.

Production Example 1 Synthesis of (dimethylsilylene) 2 (indene) 2

Under nitrogen flow, a 1 L three-necked flask receives 50 mL of THF and2.5 g (41 mmol) of Mg. To this 0.1 mL of 1,2-dibromoethane is added andthe mixture is stirred to activate Mg. After stirring for 30 minutes,the solvent is removed and 50 mL of THF is newly added. To this, asolution of 5.0 g (25.6 mmol) of 2-bromoindene in THF (200 mL) is addeddropwise over 2 hours. After completion of the addition followed bystirring at room temperature for 2 hours followed by cooling to −78° C.,a solution of 3.1 mL (25.6 mmol) of dichlorodimethylsilane in THF (100mL) is added dropwise over 1 hour. After stirring for 15 hours, thesolvent is evaporated off. The residue was extracted with 200 mL ofhexane and the solvent was distilled off to obtain 6.6 g (24.2 mmol) of2-chloromethylsilylindene (yield: 94%).

Under nitrogen flow, a 1 L three-necked flask receives 400 mL of THF and8 g of 2-chloromethylsilylindene and the mixture is cooled to −78° C. Tothis, 38.5 mL (38.5 mmol) of a solution (1.0M) ofLiN(trimethylsilylene)₂ in THF is added dropwise. After stirring at roomtemperature for 15 hours, the solvent is distilled off and the residueis extracted with 300 mL of hexane. The solvent was distilled off toobtain 2.2 g (6.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene) (indene) 2 (yield:33.4%). The results of ¹H-NMR analysis (90 MHz, CDCl₃) are as follows:δ-0.69, 0.73 (12H, dimethylsilylene), 3.66 (4H, —CH₂—), 7.17 (8H, Ar—H).

Example VIII-1 Synthesis of (dimethylsilylene) 2 (indenyl) 2 zirconiumdichloride

A Schlenk's bottle receives 22.2 g (6.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene) (indene) 2 obtained aboveand 10 mL of ether. After cooling to −78° C. and adding 9.6 mL (15.4mmol) of n-BuLi (1.6 M solution in hexane), the mixture is stirred for12 hours at room temperature. The solvent is distilled off to obtain asolid which is washed with mL of hexane to obtain a lithium saltquantitatively. This lithium salt is dissolved in 100 L of toluene. Aseparate Schlenk's bottle receives 1.5 g (6.4 mmol) of zirconiumtetrachloride and 100 mL of toluene. A 500 mL three-necked flaskreceives 100 mL of toluene, which is cooled to 0° C. To this, thelithium salt and zirconium tetrachloride in equal amounts are addeddropwise using a cannula over 1 hour. After completion of the addition,the mixture is stirred at room temperature overnight. The solution isfiltered, and the solvent in the filtrate is distilled off. The solidthus obtained was recrystallized from dichloromethane to give 1.2 g (2.4mmol) of (1,2′-dimethylsilylene) (indenyl)₂ zirconium dichloride (yield:37%).

The results of ¹H-NMR analysis (90 MHz, CDCl₃) are as follows: δ 0.85,1.08 (12H, dimethylsilylene), 7.18 (2H, —CH—), 7.2-7.4, 7.6-7.7 (8H,Ar—H).

Example VIII-2 Synthesis of (dimethylsilylene)2(3-methylindenyl) 2zirconium dichloride

A Schlenk's bottle receives 2.2 g (6.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indene)2 obtained aboveand 100 mL of ether. After cooling to −78° C. and adding 9.6 mL (15.4mmol) of n-BuLi (1.6 M solution in hexane), the mixture is stirred atroom temperature for 12 hours. The solvent is distilled off to obtain asolid, which is washed with 20 mL of hexane to obtain a lithium saltquantitatively. This lithium salt is dissolved in 100 mL of THF andcooled to −78° C. 7.4 g (52.0 mmol) of methyl iodide is added dropwiseslowly and the mixture is stirred at room temperature for 12 hours.After distilling the solvent off followed by extraction with 50 mL ofhexane, the solvent is removed to obtain 4.5 g (12 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindene)2 (yield:94%).

Subsequently, a Schlenk's bottle receives under nitrogen flow 2.0 g (5.4mmol) of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindene)2obtained above and 100 mL of ether. After cooling to −78° C. and adding13.5 mL (21.6 mmol) of n-BuLi (1.6 M solution in hexane), the mixture isstirred at room temperature for 12 hours. The solvent is distilled offto obtain a solid which was washed with hexane to obtain 1.1 g (2.9mmol) of a lithium salt. This lithium salt is dissolved under nitrogenflow in 100 mL of toluene. The mixture is cooled to −78° C. and treateddropwise with a suspension of 0.7 g (3.0 mmol) of zirconiumtetrachloride in toluene (100 mL) which has previously been cooled to−78° C. After completion of the addition, the mixture is stirred at roomtemperature for 6 hours. Thereafter, the mixture is filtered to obtain afiltrate, whose solvent is distilled off. Recrystallization fromdichloromethane gave 0.5 g (0.94 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindenyl) 2zirconium dichloride (yield: 32%). The results of ¹H-NMR analysis (90MHz, CDCl3) are as follows: δ 0.90, 1.00 (12H, dimethylsilylene), 2.89(6H, CH3), 7.2-7.7 (8H, Ar—H).

Example VIII-3 Synthesis of (dimethylsilylene) 2)-3-n-butylindenyl) 2zirconium dichloride

A Schlenk's bottle receives 0.83 g (2.4 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(indene)2 and 50 mL ofether. After cooling to −78° C. and adding 3.1 mL (5.0 mmol) of n-BuLi(1.6 M solution in hexane), the mixture is stirred at room temperaturefor 12 hours. The solvent is distilled off to obtain a solid, which iswashed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of a lithium saltas an ether adduct. This lithium salt is dissolved in 50 mL of THF andcooled to −78° C. 0.57 mL (5.3 mmol) of n-butylbromide is added dropwiseslowly and the mixture is stirred at room temperature for 12 hours.After distilling the solvent off followed by extraction with 50 mL ofhexane, the solvent was removed to obtain 0.81 g (1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindene)2 (yield:74%).

Subsequently, a Schlenk's bottle receives under nitrogen flow 0.81 g(1.77 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindene)2obtained above and 100 mL of ether. After cooling to −78° C. and adding2.7 mL (4.15 mmol) of n-BuLi (1.54 M solution in hexane), the mixture isstirred at room temperature for 12 hours. The solvent is distilled offto obtain a solid which was washed with hexane to obtain 0.28 g (1.43mmol) of a lithium salt as an ether adduct.

The lithium salt obtained above is dissolved under nitrogen flow in 50mL of toluene. The mixture is cooled to −78° C. and treated dropwisewith a suspension of 0.33 g (1.42 mmol) of zirconium tetrachloride intoluene (50 mL) which has previously been cooled to −78° C. Aftercompletion of the addition, the mixture is stirred at room temperaturefor 6 hours. Thereafter, the mixture is filtered to obtain a filtrate,whose solvent is distilled off. Recrystallization from dichloromethanegave 0.2 g (0.32 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindenyl) 2zirconium dichloride (yield: 22%).

The results of ¹H-NMR analysis (90 MHz, CDCl3) are as follows: δ 0.88,0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-1.5 (18H, n-Bu), 7.0-7.6 (8H,Ar—H).

Example VIII-4 Synthesis of (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(indenyl) 2 zirconium (diphenylbutadiene)

0.2 g (0.40 mmol) of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)bis(indenyl) 2 zirconiumdichloride and 0.09 g (0.42 mmol) of 1,4-diphenylbutadiene are combinedwith 20 mL of toluene. To this solution, 0.5 mL of n-BuLi (1.6 Msolution in hexane) is added dropwise at −78° C. After completion of theaddition, the solution is extracted with 50 mL of dichloromethane. Theextract is concentrated to 10 mL, and cooled to 0° C. whereby obtaining0.1 g of the desired product as a dark red solid (yield: 40%).

Example VIII-5

A 1 L autoclave, which had been dried by heating, was charged undernitrogen flow at room temperature with 400 mL of toluene and 3 mmol of amethyl aluminoxane. After heating to 60° C. with stirring, 3 μmol of(1,2′-dimethylsilylene) (2,1′-dimethylsilylene)(3-methylindenyl)2zirconium dichloride obtained in Example VIII-2 was added. Subsequently,the pressure was kept at 7 kg/cm²G with propylene to effectpolymerization for 1 hour. After completion of the polymerization, thereaction product was poured into methanol-hydrochloric acid solution,stirred thoroughly and filtered, and then washed thoroughly withmethanol, dried to obtain 35.0 g of an isotactic polypropylene. Thepolymer thus obtained had the melting point of 76.4° C., the intrinsicviscosity of 2.45 dl/g, the weight mean molecular weight Mw of 342,000,the molecular weight distribution Mw/Mn of 1.80 and the % meso-pentad[mmmm] of 40.7%.

A % meso-pentad was determined as a % area occupied by the signal at21.8 ppm assigned to the pentad-meso based on the total area of the 9signals appearing within the range from 19 to 22 ppm in ¹³C-NMR of thepolymer.

A melting point was determined using the following device under thefollowing conditions.

Instrument: DSC of Perkin Elmer 7 Series

Temperature raising rate: 10° C./minTemperature range: −50° C. to 150° C.

An intrinsic viscosity [η] was determined at 135° C. in decalin.

A molecular weight and a molecular weight distribution were determinedby a gel permeation chromatography (GPC) and represented as polystyrene.

Instrument: WATERS ALC/GPC150C Column: TOSO, TSK HM+GMH6×2

Solvent: 1,2,4-trichlorobenzeneFlow rate: 1 mL/min

Example VIII-6

A 1 L autoclave, which had been dried by heating, was charged undernitrogen flow at room temperature with 400 mL of toluene, 0.5 mmol ofTIBA and 1 mmol of a methyl aluminoxane. After heating to 50° C. withstirring, 1 μmol of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-n-butylindenyl) 2zirconium dichloride obtained in Example VIII-3 was added. Subsequently,the pressure was kept at 7 kg/cm² with propylene to effectpolymerization for 1 hour. After completion of the polymerization, thereaction product was poured into methanol-hydrochloric acid solution,stirred thoroughly and filtered, and then washed thoroughly withmethanol, dried to obtain 19.5 g of an isotactic polypropylene. Thepolymer thus obtained had the melting point of 71.5° C., the intrinsicviscosity of 3.18 dl/g, the weight mean molecular weight Mw of 499,000,the molecular weight distribution Mw/Mn of 1.97 and the % meso-pentad[mmmm] of 44.5%.

Example VIII-7

The procedure similar to that in Example VIII-6 was followed except forsetting the polymerization temperature at 40° C. to obtain 20.1 g of anisotactic polypropylene. The polymer thus obtained had the melting pointof 69.9° C., the intrinsic viscosity of 6.05 dl/g, the weight meanmolecular weight Mw of 914,000, the molecular weight distribution Mw/Mnof 1.95 and the % meso-pentad [mmmm] of 48.0%.

Example VIII-8

The procedure similar to that in Example VIII-3 was followed except forusing (1,2′-dimethylsilylene)(2,1′-dimethylsilylene) (indenyl) 2zirconium dichloride instead of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(3-methylindenyl)₂zirconium dichloride to obtain 30.0 g of an isotactic polypropylene. Thepolymer thus obtained had the melting point of 111.8° C., the intrinsicviscosity of 0.83 dl/g, the weight mean molecular weight Mw of 90,000,the molecular weight distribution Mw/Mn of 1.74 and the % meso-pentad[mmmm] of 66.1%.

Comparative Example VIII-1

The procedure similar to that in Example VIII-3 was followed except forusing (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)(tetrahydroindenyl)2zirconium dichloride instead of(1,2′-dimethylsilylene)(2,1′-dimethylsilylene) (3-n-butylindenyl) 2zirconium dichloride to obtain 15.6 g of an isotactic polypropylene. Thepolymer thus obtained had the melting point of 116.0° C., the intrinsicviscosity of 0.17 dl/g, the weight mean molecular weight Mw of 15,000,the molecular weight distribution Mw/Mn of 1.7 and the % meso-pentad[mmmm] of 75.7%.

INDUSTRIAL APPLICABILITY

A propylenic polymer which has an excellent melt flowability, contains aless amount of stickiness-causing components, has a low modulus and ispliable, and is capable of providing a transparent molded article, thusbeing useful as a substitute for a pliable vinyl chloride resin and acomposition thereof are thus provided. They are excellent also in termsof the heat seal performance at a low temperature, as well as thetransparency and the rigidity.

1-15. (canceled)
 16. A method for producing a propylene homopolymer,comprising: homopolymerizing propylene in the presence of apolymerization catalyst, to obtain said propylene homopolymer, saidpolymerization catalyst comprising: (A) a transition metal compoundrepresented by Formula (I) shown below and (B) is at least one componentselected from the group consisting of (B-1) or (B-2), wherein (B-1) is acompound which forms an ionic complex by reacting with a transitionmetal compound as a component (A) or a derivative of the component (A),and (B-2) is an aluminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same as or different from each other,X denotes a σ-binding ligand, and, when two or more Xs are present theymay be the same or different, and each may be linked with another X, E¹,E² or Y; Y denotes a Lewis base, and, when two or more Ys are presentthey may be the same or different, and each may be linked with anotherY, E¹, E² or X, each of A¹ and A² denotes a divalent crosslinking groupcombining two ligands including a hydrocarbon group having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group, a germanium-containing group,a tin-containing group, —O—, —CO—, —S—, —SO₂—, —Se—, —NR—, —PR—,—P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms and a halogen-containinghydrocarbon group having 1 to 20 carbon atoms, and each may be the sameas or different from each other; q is an integer of 1 to 5 andrepresents (valency of M)−2, and r is an integer of 0 to 3; wherein saidpropylene homopolymer satisfies the following requirements (1) and (2):(1) the amount of the components which are dissolved out into hexane at25° C. (H25) ranges from 0 to 80% by weight; and, (2) no melting point(Tm(° C.)) is observed in DSC or, when any Tm is observed then the Tmand the fusion endothermic calorie ΔH(J/g) are in the relationshiprepresented by the following formula:ΔH≧6×(Tm−140).
 17. A method for producing a propylenic copolymer whereinpropylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms iscopolymerized in the presence of a polymerization catalyst comprising:(A) a transition metal compound represented by Formula (I) shown belowand (B) is at least one component selected from the group consisting of(B-1) and (B-2), wherein (B-1) is a compound which forms an ioniccomplex by reacting with a transition metal compound as a component (A)or a derivative of the component (A), and (B-2) is an aluminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same as or different from each other,X denotes a σ-binding ligand, and, when two or more Xs are present theymay be the same or different, and each may be linked with another X, E¹,E² or Y; Y denotes a Lewis base, and, when two or more Ys are presentthey may be the same or different, and each may be linked with anotherY, E¹, E² or X, each of A¹ and A² denotes a divalent linking groupcombining two ligands including a hydrocarbon group having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group, a germanium-containing group,a tin-containing group, —O—, —CO—, —S—, —SO₂—, —Se—, —NR—, —PR—,—P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms and a halogen-containinghydrocarbon group having 1 to 20 carbon atoms, and each may be the sameas or different from each other; q is an integer of 1 to 5 andrepresents (valency of M)−2, and r is an integer of 0 to 3; wherein saidpropylenic copolymer satisfies the following requirements (1) and (2):(1) the stereoregularity index (P) determined by a ¹³C-NMR ranges from55 to 90% by mole; and, (2) the amount of the components which aredissolved out at 25° C. or lower (W25) in a temperature-raisingchromatography ranges from 20 to 100% by weight. 18-64. (canceled)
 65. Amethod for producing a propylene homopolymer, comprising:homopolymerizing propylene in the presence of a polymerization catalyst,to obtain said propylene homopolymer, said polymerization catalystcomprising: (A) a transition metal compound represented by Formula (I)shown below and (B) is at least one component selected from the groupconsisting of (B-1) or (B-2), wherein (B-1) is a compound which forms anionic complex by reacting with a transition metal compound as acomponent (A) or a derivative of the component (A), and (B-2) is analuminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same to as or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be the same or different, and each may be linked withanother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be the same or different, and each may be linkedwith another Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group combining two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be the same as or different from each other; q is aninteger of 1 to 5 and represents (valency of M)−2, and r is an integerof 0 to 3; wherein said propylene homopolymer satisfies the followingrequirements (1) to (3): (1) the amount of the components which aredissolved out at 25° C. or lower (W25) in a temperature-raisingchromatography ranges from 20 to 100% by weight; (2) the amount of thecomponents which are dissolved out into hexane at 25° C. (H25) rangesfrom 0 to 80% by weight; and, (3) no melting point (Tm(° C.)) isobserved in DSC or, when any Tm is observed then the Tm and the fusionendothermic calorie ΔH(J/g) are in the relationship represented by thefollowing formula:ΔH≧6×(Tm−140).
 66. A method for producing a propylene homopolymer,comprising: homopolymerizing propylene in the presence of apolymerization catalyst, to obtain said propylene homopolymer, saidpolymerization catalyst comprising: (A) a transition metal compoundrepresented by Formula (I) shown below and (B) is at least one componentselected from the group consisting of (B-1) or (B-2), wherein (B-1) is acompound which forms an ionic complex by reacting with a transitionmetal compound as a component (A) or a derivative of the component (A),and (B-2) is an aluminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same to as or different from eachother, X denotes a 6-binding ligand, and, when two or more Xs arepresent they may be the same or different, and each may be linked withanother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be the same or different, and each may be linkedwith another Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group combining two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be the same as or different from each other; q is aninteger of 1 to 5 and represents (valency of M)−2, and r is an integerof 0 to 3; wherein said propylene homopolymer satisfies the followingrequirements (1) to (3): (1) the meso-pentad fraction (mmmm (inpercentage terms by mole)) ranges from 20 to 60% by mole; (2) theracemi-pentad fraction (rrrr) and (1−mmmm) are in the relationshiprepresented by the following formula:[rrrr/(1−mmmm)]≦0.1 wherein the racemi-pentad fraction (rrrr) and themeso-pentad fraction (mmmm) are not in percentage terms; and, (3) theamount of the components which are dissolved out at 25° C. or lower(W25) in a temperature-raising chromatography ranges from 20 to 100% byweight.
 67. A method for producing a propylene homopolymer, comprising:homopolymerizing propylene in the presence of a polymerization catalyst,to obtain said propylene homopolymer, said polymerization catalystcomprising: (A) a transition metal compound represented by Formula (I)shown below and (B) is at least one component selected from the groupconsisting of (B-1) or (B-2), wherein (B-1) is a compound which forms anionic complex by reacting with a transition metal compound as acomponent (A) or a derivative of the component (A), and (B-2) is analuminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same to as or different from eachother, X denotes a σ-binding ligand, and, when two or more Xs arepresent they may be the same or different, and each may be linked withanother X, E¹, E² or Y; Y denotes a Lewis base, and, when two or more Ysare present they may be the same or different, and each may be linkedwith another Y, E¹, E² or X, each of A¹ and A² denotes a divalentcrosslinking group combining two ligands including a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing group, agermanium-containing group, a tin-containing group, —O—, —CO—, —S—,—SO₂—, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atomsand a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,and each may be the same as or different from each other; q is aninteger of 1 to 5 and represents (valency of M)−2, and r is an integerof 0 to 3; wherein said propylene homopolymer has a molecular weightdistribution (Mw/Mn) determined by a gel permeation chromatography (GPC)of 4 or less and/or an intrinsic viscosity [η] determined in a tetralinsolvent at 135° C. of 0.5 to 15.0 dl/g.
 68. A method for producing apropylenic copolymer, comprising: copolymerizing propylene and ethyleneand/or an α-olefin having 4 to 20 carbon atoms in the presence of apolymerization catalyst, said polymerization catalyst comprising: (A) atransition metal compound represented by Formula (I) shown below and (B)is at least one component selected from the group consisting of (B-1)and (B-2), wherein (B-1) is a compound which forms an ionic complex byreacting with a transition metal compound as a component (A) or aderivative of the component (A), and (B-2) is an aluminoxane:

in which M denotes a metal element of Group 3 to Group 10 or oflanthanoids in the periodic table, each of E¹ and E² denotes a ligandselected from a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amide group, a phosphide group, ahydrocarbon group and a silicon-containing group is linked with eachother via A¹ and A² and may be the same as or different from each other,X denotes a σ-binding ligand, and, when two or more Xs are present theymay be the same or different, and each may be linked with another X, E¹,E² or Y; Y denotes a Lewis base, and, when two or more Ys are presentthey may be the same or different, and each may be linked with anotherY, E¹, E² or X, each of A¹ and A² denotes a divalent linking groupcombining two ligands including a hydrocarbon group having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group, a germanium-containing group,a tin-containing group, —O—, —CO—, —S—, —SO₂—, —Se—, —NR—, —PR—,—P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms and a halogen-containinghydrocarbon group having 1 to 20 carbon atoms, and each may be the sameas or different from each other; q is an integer of 1 to 5 andrepresents (valency of M)-2, and r is an integer of 0 to 3; wherein saidpropylenic copolymer has a molecular weight distribution (Mw/Mn)determined by a gel permeation chromatography (GPC) of 4 or less and/oran intrinsic viscosity [1] determined in a tetralin solvent at 135° C.of 0.5 to 15.0 dl/g.